Teza Furan Christofidis-2007

Cranfield University
Cranfield Health
Master by Research
Academic Year 2004/2006
Stavros Christofidis
Analytical Methods For Assessing Paper Degradation In Transformers
Supervisors: Dr Setford
Dr Ritchie
Dr Aldred
May 2006
This thesis is submitted in partial fulfilment of the requirements for the degree of
Master by Research
© Cranfield University, 2006. All rights reserved. No part of this publication may be
reproduced without the written permission of the copyright holder
1
ACKNOWLEDGMENTS
I would like to thank Dr Setford and Dr Ritchie for supervising this work.
My gratitude to Dr Mavrommatis for giving me the oppurtunity to undertake
this project and particular thanks to NYNAS Naphthenics for providing me with all
the appropriate equipment and materials for the completion of the project.
Finally my deepest gratidude to my family who have encouraged me and
supported me throughout this MRes.
2
ABSTRACT
Power transformers are essential equipments for distributing electricity.

However, maintenance of these equipments is necessary to ensure long working life
and to avoid catastrophic incidents.
Insulation of the instrument is essential, and mainly consists of mineral oil and
cellulosic paper.
This research work investigates and examines in a series of different
experiments the compounds produced from the degradation of the cellulosic paper,
known as furanic compounds.
Five furanic derivatives (5-HMF, 2-FAL, 2-ACF, 5-MEF and FOL) were
examined, and it was established throughout this work that these furanic compounds
degradate faster in aqueous solution, under a controlled environment, than in an
organic, it is possible to produce from one furanic compound other derivatives, and
finally each furanic compound distributes differently in an oil water environment,
affecting the recovery of each individual.
The knowledge obtained from this research work can be used for the
development of the existing method of analysis of furanic compounds, and help to
provide a better diagnosis of the insulation state of the transformer.
3
TABLE OF CONTENTS
TABLE OF TABLES...................................................................................................6
TABLE OF FIGURES.................................................................................................7
1.0 INTRODUCTION ...............................................................................................10
1.1 Transformers ................................................................................................10
1.2 Insulating oil ................................................................................................12
1.3 Insulating Paper ...........................................................................................13
1.4 Degradation of Insulating paper...................................................................14
1.4.1 The Paper Degradation Process ...........................................................15
1.4.1.1 Effect of Temperature ..........................................................................16
1.4.1.2 Effect of Oxygen..................................................................................17
1.4.1.3. Effect of Moisture ............................................................................18
1.5 Furanic compounds ......................................................................................19
2.0 AIM, BACKGROUND AND THE SCOPE OF THE PROJECT..................27
3.0 IDENTIFICATION OF FURANIC COMPOUNDS AND
CALIBRATION USING DIFFERENT ANALYTICAL TECNIQUES...............31
3.1 Aim ..............................................................................................................31
3.2.0 Materials and Methods.................................................................................31
3.2.1 General Materials.................................................................................31
3.2.2 Method for the Maximum Absorbance................................................32
3.2.3 Calibration and Analysis Using HPLC, Infrared and Fluorescence
Spectroscopy Techniques.....................................................................................32
3.3 Results..........................................................................................................34
3.3.1 Initial Scanning of Absorbance of furanic compounds using UV-Vis
spectroscopy.........................................................................................................34
3.3.2 Calibration Results & Graphs of the five furans using UV-Vis
Spectroscopy. .......................................................................................................35
3.3.3 Spectra of the five furanic compounds using Near Infrared
Spectroscopy. .......................................................................................................40
3.3.4 High Performance Liquid Chromatography results for standard furan
compounds analysed. ...........................................................................................43
3.3.5 Results obtained for the five furanic compounds using Fluorescence
spectroscopy analysis...........................................................................................46
4
3.4 Discussion ....................................................................................................49
3.5 Conclusion ...................................................................................................51
4.0 AGEING, STABILITY & DEGRADATION PRODUCTS.......................54
4.1 Aim ..............................................................................................................54
4.2 Materials and Methods.................................................................................54
4.2.1 Materials ..............................................................................................54
4.2.2 Method .................................................................................................55
4.3 Results & Discussion ...................................................................................57
4.3.1 Ageing results in aqueous environment ...............................................58
4.3.2 Ageing results of the furanic compounds in acetonitrile and methanol
………………………………………………………………………..73
4.3.3 Results from the precipitation matter and the solutions at all pH at 60˚C
and 80˚C...............................................................................................................91
4.4 Conclusion ...................................................................................................95
5.0 SUMMARY OF CONCLUSIONS AND FUTURE WORK ......................97
APPENDIX A...……………………………………………………………………..99
A. RECOVERY & DISTRIBUTION OF FURANIC COMPOUNDS .....................105
A.1 Aim..................................................................................................................105
A.2 Materials and method......................................................................................105
A.2.1 Materials...................................................................................................105
A.2.2 Method .....................................................................................................105
A.3 Results .............................................................................................................106
A.4 Discussion .......................................................................................................112
A.5 Conclusion ......................................................................................................114
APPENDIX B TABLES OF AGEING RESULTS FOR THE FIVE FURAN
DERIVATIVES AT DIFFERENT CONDITIONS FOR 63 DAYS OF
ANALYSIS.
………………………………………………………………………………116
5
TABLE OF TABLES
Table 1 Initial Scanning of the five furan derivatives using UV spectroscopy. The
highlighted numbers are indicating the wavelength that gives the highest
absorbance…………………………………………………………………………..
Table 2 Spectrophotometric response of the five furanic compounds in different
concentrations at their maximum adsorption using UV spectroscopy……………...
Table 3 Peak area results for the five furanic compounds of different concentration
solutions usingHPLC. The results obtained by identifying and integrating each peak
from the spectrum to determine the peak area of the appropriate furan. .....................43
Table 4 Illustration of the different conditions that the furanic compounds will be
investigated for the purpose of ageing, stability and degradation analysis..................55
Table 5 Results from the calibration of the five furanic compounds under HPLC
analysis……………………………………………………………………………..
Error! Bookmark not defined.
Table 6 Results of a series of different solutions used for the calibration of the furan
derivatives by HPLC...................................................................................................74
Table 7 Results for the ageing of 5-HMF in Acetonitrile and Methanol.....................80
Table 8 Results for the ageing of 2-FAL in Acetonitrile and Methanol......................83
Table 9 Results for the ageing of 2-ACF in Acetonitrile and Methanol......................85
Table 10 Results for the ageing of 5-MEF in Acetonitrile and Methanol. .................87
Table 11 Results for the ageing of FOL in Acetonitrile and Methanol……………. 89
Table 12 Results from the precipitation matter formed and also from the solutions
filtered for each furan derivative in all pH at 60 C and 80 C using HPLC…………93
Table 13 Recovery results for 5-HMF after two extractions indicating the total
concentration recovered with the percentage that corresponded to the extraction… 107
Table 14 Recovery results for 2-FAL after two extractions indicating the total
Table 15 Recovery results for 2-ACF after two extractions indicating the total
Table 16 Recovery results for 5-MEF after two extractions indicating the total
Table 17 Recovery results for FOL after two extractions indicating the total
6
TABLE OF FIGURES
Figure 1 Cellulose; Two units of D-anhydroglucopyranose joined together by β-1,4-
glycosidic bonds...........................................................................................................15
Figure 2 Thermal degradation of insulating paper.......................................................17
Figure 3 Oxidation of Cellulose..................................................................................18
Figure 4 Hydrolytic degradation of cellulose ..............................................................19
Figure 5 furan and derivatives .....................................................................................20
Figure 6 Physical properties of furan derivatives (adapted from Ulmann's
Encyclopedia 6th Ed). ..................................................................................................20
Figure 7 Production of 2-furfural from cellulose (adapted from Shafizadeh and Lai).
......................................................................................................................................21
Figure 8 Production of 2-furfural from lignin (adapted from Shafizadeh and Lai).....22
Figure 9 Production of furan from pentose (adapted from R.O.C Norman)................22
Figure 10 Calibration Graphs of the five furans by UV-Visible spectrophotometer. (a)
5-HMF, (b) 5-MEF, (c) 2-ACF, (d) 2-FAL and (e) FOL. ...........................................39
Figure 11Infrared Spectra of the five furans in Tetrachloroethylene solution. (a) 2-
ACF, (b) 2-FAL, (c) FOL, (d) 5-HMF and (e) 5-MEF................................................42
Figure 12 Calibration Graphs of the five furanic compounds by HPLC. (a) 5-HMF, (b)
2-FAL, (c) 2-ACF, (d) 5-MEF and (e) FOL ................................................................45
Figure 13 Fluorescent spectra of the five furanic compounds when they were scan
from 190 – 900cm-1, each one at a different excitation wavelength. ...........................48
Figure 14 Calibration graphs of the five furanic compounds in water using UV-Vis
spectroscopy; (a) 5-HMF, (b) 2-FAL, (c) 2-ACF, (d) 5-MEF and (e) FOL. ...............62
Figure 15 Ageing of 5-HMF at different pH under different temperatures. ................64
Figure 16 Ageing of 2-FAl at different pH under different temperatures. ..................66
Figure 17 Ageing of 2-ACF at different pH under different temperatures..................68
Figure 18 Ageing of 5-MEF at different pH under different temperatures. ................70
Figure 19 Ageing of FOL at different pH under different temperatures. ....................72
Figure 20 Ageing progress of 5-HMF in (a) Acetonitrile and (b) Methanol over time.
......................................................................................................................................81
Figure 21 Ageing progress of 2-FAL in (a) Acetonitrile and (b) Methanol over time.
......................................................................................................................................84
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Figure 22 Ageing progress of 2-ACF in (a) Acetonitrile and (b) Methanol over time.
......................................................................................................................................86
Figure 23 Ageing progress of 5-MEF in (a) Acetonitrile and (b) Methanol over time.
......................................................................................................................................88
Figure 24 Ageing progress of FOL in (a) Acetonitrile and (b) Methanol over time. ..90
8
CHAPTER ONE
INTRODUCTION
AND
LITERATURE REVIEW
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1.0 INTRODUCTION
Electricity is essential to humanity in order to provide our daily lives and working
environment with essential energy, ultimately leading to a higher quality of life.
Power Transformers are used world wide for the transmission and distribution of high
voltage electrical energy over long distances with minimum power losses and at least
cost [1]. The power transformation process involves increasing and/or decreasing
voltage levels according to the need of the consumer, using a power transformer.
Essentially, transformers are crucial to the transfer of electrical energy from the
production point to the point where the energy will be consumed. This is achieved by
using high voltages for transmission purposes, followed by stepping down of the
voltage levels for distribution to the consumer.
1.1 Transformers
Generally, the operation theory of a transformer is based upon three principles:
A voltage is delivered to the primary winding via a conductor, which

generates a magnetic field within the transformer core.
The magnetic field around the core will be producing an induction current
within the secondary winding
This secondary winding current is used as an output of the electrical

energy to the transmission lines.
There are many different types of transformers including: Generator transformers;

Transmission transformers; Distribution transformers; Transformers for DC converter
stations; and Earthing transformers. As described above, all the transformers operate
under the same principles but in general they can be divided into two major categories
from the design point of view: the shell type and the core type.
10
In a core type transformer, the core is made of laminated magnetic steel and its role is
to reduce the current drawn by the transformer from the system when it is off load.
The core is surrounded with windings (high voltage or low voltage) that are
cylindrical in form. The type of configuration can be as a disc, a layer or even a foil.
No matter which configuration is used, the manufacturer always considers the
alignment to provide the best cooling process of the system and also the better
insulation by the oil. A transformer may contain from one up to three cores (in the
case of a three phase transformer), with all cores connected with laminated magnetic
steel, the same material used for the production of the core.
In the shell type transformer, the configuration of the laminated magnetic steel of the
core is square or rectangular having slots for the windings to be arranged, which again
may be of high and low voltages [2].
When it comes to the production of a transformer the designer and the

engineer need to consider several factors in order to achieve a suitably long working
life for the transformer. A well designed transformer will exhibit fewer faults,
maximum system performance and also to be able to take heavy load whenever is
required. These design aspects may include the winding connection, tappings and tap
changers including the types of connection, the function of on load tap changer, the
transformer impedance, the thermal design, insulation, the cooling system, the
electrical and mechanical design, and finally parameters designed to protect the
transformer during normal operation (moisture, overload, electrical) [2].
The insulating material of a transformer mainly consists of cellulosic paper

wrapped around the conductor impetrated in mineral oil, the latter acting both as
coolant and as a dielectric element. These two materials are essential for the efficient
operation of the transformer and are especially important with respect to insulation.
Insulation is a critical issue because it will determine the effective working lifetime of
the transformer. Any fault to the system will be a result from its insulation. It is vital
to monitor the insulation condition of the transformer in order to predict any
malfunction and to resolve the problem before transformer failure. A single problem
on a transformer can not only cause problem to the individual unit, but may cause
major faults to the whole circuit, with the worst outcome being a total system
11
shutdown. On such occasions the treatment is significantly more costly than repair of
a single transformer unit and requires more time to be resolved.
1.2 Insulating oil
Mineral oil is used for the insulation of a transformer and can be classified into
two categories; the paraffinic and the naphthenic. The naphthenic oil is the crude oil
used at the refinery for the production of the transformer oil, which later can be used
as insulating matter to the transformer [3]. Paraffinic refined oil has low physical
properties and may produce oxidation products which can lead to sludge forming in
the windings and furthermore to blockage of the ducts in a transformer. Naphthenic
oil will allow those oxidation products to be dissolved. Therefore, it is essential to
reduce the rate of oxidation of the oil, such as by using antioxidant reagents or
enhancing the existing antioxidants by ‘hydrogenation’. Such approaches have been
shown to confer a longer working life on the transformer [3].
The oil in the transformer, apart from its insulation properties, has other useful
functions such as;
Cooling
Electrical insulation
Information carrier
Besides those functions (physical, chemical) the oil which will fulfill the requirements
of the power transformation process, must follow certain requirements from the point
of Environmental Legislation and Health and Safety. International Standards and
National specifications are often listed with the minimum requirements expected from
the oil. The most common standards are IEC 60296 and ASTM D3487. National
specifications are often used from the transformer producers according to their own
needs [2].
12
1.3 Insulating Paper
Solid insulation of a transformer is commonly provided by cellulosic paper

which is impregnated with the oil. The paper is made by the delignification of wood
pulp by the Kraft process [2, 3, and 4]. Like the insulating oil, cellulosic paper also
provides useful functions to the circuit, such as;
Electrical insulation
Mechanical stability
Creation of space
Direction of oil flow
Also, cellulosic paper is used due to highly compatibility with the mineral oil, giving
an overall increase in beneficial electrical and physical properties over and above that
exhibited by each individual material.
Insulating paper consists of 76-86% w/w cellulose, 10-15% w/w hemi

cellulose, 4-8% w/w lignin and 0.2-0.8% w/w mineral substances [2]. The thickness
of the paper varies from 30-120mm, with natural moisture content of 6% [3]. The
paper is wound onto the copper (material used for the production of the conductor)
before the coils are formed, separating each turn with the next.
Before the paper is introduced to the transformer, there is in a high necessity to

reduce the percentage of moisture content. The process involves drying of the paper
under vacuum at 95-100˚C for 10-16 days, reducing the final moisture content to less
than 0.1% [3].
International Material Standards also exist to establish the requirements for

the choice of the paper which will be used for the insulation of a transformer. The
most common standards are IEC 60554 and ASTM D 1305 [2].
Insulation paper is a key material to the operational life-time of a transformer.

It is expected to last until the end of the working life of the circuit (typically 25 years)
13
and the choice of the type is critical. The most preferred type of paper is the Kraft
paper because of its high purity and its specific electrical resistivity. During paper
production, it must be ensured that there are no metal ions present, which will
otherwise affect the insulation performance of the paper. Economically, Kraft paper
is a cheap source of insulation, something that needs to be considered when
considering the fact that a typical power transformer requires 10-12 tonnes of this
material, in the case of poor insulation properties.
1.4 Degradation of Insulating paper
The Kraft paper used in electrical transformers degrade over the time of
operation, and the rate of degradation depends on the prevailing thermal, oxidative,
hydrolytic, electrical and mechanical conditions within the transformer [5]. Normally,
the operating temperature for a power transformer is between 80-100˚C, and even at
these relatively modest temperatures, the insulating paper can undergo a slow
degradation, with a resultant loss in its mechanical and electrical properties.
Consequently, the degradation of the insulating paper has an effect on the tensile
strength of the paper by decreasing the degree of polymerization (DP) of cellulose [6].
Typically, an unaged paper has a DP value, which is the number of the monomeric
units (anhydroglucose) in the cellulose chain [12], between 1000 and 1300 [7, 8].
After the reprocessing of the paper, by means of drying, the DP value decreases to
950, and ageing of the paper further decreases the DP value to 500 [8]. Over this
range (950-500 DP) the tensile strength of the paper is in relatively good condition
and offers constant high-quality insulation to the transformer. In the case where the
DP value reduces to 150 or lower, the tensile strength of the paper has decreased to
20% of its initial value and therefore the paper has very poor strength properties [7-
10].
14
The degradation of insulating paper can initiate a major fault in a transformer
by many different mechanisms:
The paper can break away from the transformer windings and block
ducts
Water is produced from the degradation products which can affect the
resistivity of the paper and the voltage breakdown of the oil.
The worst scenario is the production of low molecular weight carbon
species from the paper which increases system conductivity and causes
overheating and conductor faults [10].
1.4.1 The Paper Degradation Process
As mentioned above, degradation of paper is a result of the reduction of the

degree of polymerization of cellulose. Cellulose is one of a number of natural
polymers of glucose. Glucose units, and more precise D-anhydroglucopyranose, are
combined together to form long chain polymers held together by covalent bonds,
specifically β-1,4-glycosidic bond linkages [12]. Figure 1 represents the chemical
structure of cellulose. A number of cellulose chains may be held together by
extensive intermolecular hydrogen bonding which confers a degree of crystalline
structure of the cellulose molecule aggregates. The formation of a single cellulose
fibre provide the paper its mechanical strength due to the formation of those
intramolecular and intermolecular (hydrogen bonds), and also, due to the formation of
a micro crystalline structure.
H H
H
HO OH O
O CH2OH O
H H
H
H O O
CH2OH
OH OH
H H
H
Figure 1 Cellulose; Two units of D-anhydroglucopyranose joined together by β-1,4-glycosidic

bonds
15
The length of the cellulose molecule is measured in terms of the degree of
polymerization, which as it was mentioned earlier is the average number of glucose
units per cellulose molecule [12].
In general the process of cellulosic degradation involves a chain scission or

depolymerization of the cellulose chain, and the release of a different number of
products [4], typically:
Hydrogen
Hydrocarbons
Carbon monoxide
Carbon dioxide
Water
Furanic compounds [4].
Principally, the formation of specific products and hence, the degradation mechanism
employed depends upon the conditions to which cellulosic degradation is subjected.
Predominantly, there are three main factors which promote degradation, which will be
discussed in the proceeding sections:
Temperature
Oxygen and oxidizing agents
Moisture [12].
1.4.1.1 Effect of Temperature
Degradation is a chemical process and thus should obey the Arrhenius theory
of reaction kinetics, which relates the log of the reaction constant to the reciprocal of
the absolute temperature [13]. Values for the activation energy of degradation of
cellulose in oil range, of the order of 85 KJ/mole for the oxidative degradation
reaction, to 120 KJ/mole for the hydrolytic degradation reaction [7, 14-15]. It is
16
suggested that at about 140˚C and above, the rate of degradation increases
significantly, implying a change in the activation energy [15-16].
Cellulose, under higher temperature (to a maximum of 200˚C) tends to be

degraded via destruction of the 1, 4 glycosidic bonds to produce free glucose,
moisture, carbon oxides and organics acids, see figure 2.
CH2OH OH CH2OH
O O
O OH O O
HO OH
OH OH OH Heat
OH CH2OH
O O + OH2 + CO2 + CO
OH
Figure 2 Thermal degradation of insulating paper
1.4.1.2 Effect of Oxygen
The second cause of paper degradation is oxygen, which can enter through the
open breather system of the transformer, or the faulty seals and though the oil to affect
the insulating paper. Fabre and Pichon et al. [17] explain that oxygen increases the
rate of degradation of insulating paper which can be up to a factor of approximately
2.5. Reducing the oxygen level in oil below 30,000 ppm reduces the rate of
degradation by a factor of approximately 16. Cellulose is highly susceptible to
oxygen and oxidising agents. Acid attacks the hydroxyl groups of the cellulose,
oxidising them to carbonyl and carboxyl groups. This process weakens the glycosidic
bonds and can lead to chain scission. Moisture is also produced during this oxidative
process. Figure 3 illustrates the oxidation reaction process [12, 17].
17
CH2OH OH CH2OH
O O
O OH O Oxygen
OH OH OH
O O
OH CH2OH OH
COOH OH CHO
O O
O OH O
OH OH
O OH + OH2
O
OH COOH OH
Figure 3 Oxidation of Cellulose
1.4.1.3. Effect of Moisture
The final and probably the most serious cause of accelerated paper degradation
is water. Moisture, like oxygen, can enter the transformer via the main tank, through
the open breather system as well as via any leaking gaskets. Also, if the paper
undergoes thermal or oxidative degradation, moisture is produced, and hence
hydrolytic degradation is promoted. The water in the transformer can be found
mainly in three forms;
Dissolved as a solution
Suspended in emulsion
As free water [18].
Water reduces the insulating properties of the paper and more importantly it
reduces the tensile strength. When moisture attacks the cellulose, it can break the
glycosidic bonds releasing free molecules of glucose (Fig 4). It is proposed that
cellulosic paper in equilibrium with the atmosphere approximately contains 7 to 8%
moisture by weight [12]. Other investigations showed that new transformers are
usually specified between 0.5 and 1% of moisture content. Therefore, it is essential
that the paper prior to installation at the transformer is carefully dried out to minimise
the rate of degradation [18].
18
CH2OH OH CH2OH
O COOH
O O O
OH O Water OH
OH OH OH
O O OH OH
OH CH2OH OH
OH
free glucose
Figure 4 Hydrolytic degradation of cellulose
1.5 Furanic compounds
The cellulosic insulating paper can be degradated by the effect of the three
factors described in the preceeding Section. When degradation occurs one of the
products that it is formed is the family of compounds known as the furans.
Furan is the parent compound of these five membered ring structures

containing one oxygen atom. Some of the physical properties associated with this
family of compounds include low boiling point, high flammability, a strong ether
odour and miscibility with most organic solvents. Furan shows some aromatic
characteristics arising from the delocalization of the four π electrons and one electron
from the oxygen pairs [19]. Since they are electron rich heterocycles, these
compounds can undergo polymerization; they can produce other furan derivatives by
cyclodehydration, they can undergo the Michael reaction, acting as nucleophiles, and
finally can undergo the Diels-Alder reaction [20-21].
There are many different types of furan derivatives, but in this project we will
examine the following five, since they are the main derivatives examined from the
existing method for determining the insulation state of the transformer:
5-hydroxymethyl-2-furfuraldehyde (5-HMF)
2-furfuraldehyde (2-FAL)
2-acetyl furan (2-ACF)
5-methyl-2-furfuraldehyde (5-MEF)
Furfuryl alcohol (FOL)
19
Below are illustrations of the chemical structures of the furan and the five
derivatives, following with a table of some of their physical properties.
OHCH2 CHO
O O CHO
O
Furan 5-hydroxymethyl-2-furfuraldehyde 2-furfuraldehyde
COCH3 H3C CHO CH2OH

O O O
2-acetyl furan 5-methyl-2-furfuraldehyde furfuryl alcohol
Figure 5 furan and derivatives
CAS Mp, Bp, ˚C Ρ(20˚C), N20D Vapor Flash Explosion Ignition Solubility Dielectric Viscosity
Registry ˚C g/cm3 Density Pointa, Limits in Temperature, in H2O constant (25 ˚C)
number (air=1) ˚C air, vol % ˚C (25 ˚C) (20 ˚C) mPa.s
Wt %
furfural (98-01- - b
1) 36.5
161.6 1.1598 1.5261 3.3 61.7 2.1- 315 8.3 41.9 1.49
19.3
Furfuryl alcohol (98-00-
0)
-29 170 1.1285 1.4868 3.4 77 1.8- 391 ∞ 5.0
16.3
furan (110- - 31.36 0.9178 1.4214 2.36 - 2.3- 282 1 6.24
00-9) 85.6
33.5 14.3
Tetrahydrofurfuryl-
alcohol
(97-99-
4)
<-
80
178 1.0511 1.4520 3.52 83.9e 1.5- ∞ 13.6
9.7
2-Methylfuran (534- - 64 0.913 1.4320 -27 <0.3
22-5) 88.7
2-Methyltetra- (96-47- - 80.2 0.854 1.4025 11.1 15.1
hydrofuran 9) 136
Dihydropyran (110- -70 84 0.923 1.4380 - 1.6
87-2)
17.8
Figure 6 Physical properties of furan derivatives (adapted from Ulmann's Encyclopedia 6th Ed).
It was mentioned above (see section 1.3) that insulating paper contains
cellulose, lignin, mineral substances, and therefore all the three constituents under
degradation process can produce furans. Production of furans can also be generated
20
from pentozans. Figure 7, 8, 9, shows the chemical reactions for the production of
furans from cellulose, lignin and pentozans respectively.
CH2OH OH CH2OH H OH
O O - H20
O OH O
OH OH
RO OR
O OH
O O
OH CH2OH OH
OHCH2
R R +H2O
-ROH
OH
CHO
O CH2OH O HC CHO
OHC - H2O
CH -ROH RO
CH HC OH
HC OH
C OH C OH
H2 H2
- CH2OH
OHC O
2-Furfural
Figure 7 Production of 2-furfural from cellulose (adapted from Shafizadeh and Lai).[22]
21
O O H2 OH
H2C
C
HO O O O C CHO
HO H
HO
HO
HO OH
HO
H
H
HO OH
O - H2O O OH OH
O O
O CH
CH2OH CH2OH
HO OH
HO OH
O CHO
2-Furfural
Figure 8 Production of 2-furfural from lignin (adapted from Shafizadeh and Lai).[22]
H H
CHOH CHOH CHOH C + CHOH C
- H2O H
CHOH HO CH2 +
CH2OH CHO
HO CHO H2O CH2 HO
CHO
+
- H20 -H
- H2O HO H
O CHO H
O CHO
H
2-Furfural
Figure 9 Production of furan from pentose (adapted from R.O.C Norman).[23]
The similarity between the three processes is the end product, which is 2-FAL.
Only in the degradation of cellulose is 5-HMF produced prior to 2-FAL. In the case
of the degradation of lignin it was found that after the production of 2-FAL further
22
degradation produces FOL but in a lower magnitude than 2-FAL [24]. When
pentosans are degraded it was found that around 4 times more 2-FAL is produced
when compared to cellulose degradation. The important issue regarding the
degradation of pentosans is that 5-HMF is not detected. The only explanation to that
difference is that 5-HMF is produced as a degradation product from hexoses, such as
glucose, while 2-FAL is produced from acid hydrolysis of pentosans [24].
It is known that degradation of cellulosic insulating paper by the factors and

processes described above result in the reduction of the mechanical strength of the
paper by reducing the length of the cellulose molecules and therefore reducing the
degree of polymerization [12]. Correspondingly it has been found that there is a
relationship between DP and furfuraldehydes. Chendong [31], Scholink [31],
Pahlavanpour [31] and De Pablo [25, 31] developed a series of equations in order to
express the correlation of DP with the production of 2-Fal. De Pablo [25] build a
degradation model based on experimental data and field measurements from a
research programme carried out for CIGRE (International Council on Large Electric
Systems) and found that for every three cellulose chain scissions one furfural
molecule is produced. Below are the four mathematical approaches which link the
DP with the production of Furfurals:
(Chendong) DP= (1.51-Log102-FAL)/0.0035 (1)

(Scholnik) DP= (1.17-Log102-FAL)/0.00288 (2)
(Pahlavanpour) DP=800/ (0.186*2-FAL) +1 (3)
(DePablo) DP = 7100 / 8.88 + 2FAL (4)
These formulae correlates the amount of 2-FAL, expressed in mg/kg of the oil to the
DP of the cellulosic paper in the windings of a given transformer. Rearranging
equations (1) and (2) as Log2-FAL versus DP and equations (3) and (4) as 1/DP
versus 2-FAL is possible to obtain linear plots [31]. It has been established that the
lower limit that the DP can reach before significant transformer problems are
encountered is 150 units, and by using De Pablo formula, it was found that the
maximum amount of 2-FAL that can be generated is 30 mg/kg, the same value
reported by CIGRE members. A problem with the formula was that it does not take
account of the fact that the winding paper is not degraded to the same extent under
23
different conditions, notably temperature. For example, the innermost layers of the
winding conductor degrade twice as fast as the outer layers. Other formulae have
been developed in order to express the relation of DP versus furfural production under
different conditions [27]. For instance, it can be assumed that in an normal operating
transformer 20% of winding conductor insulation degrade twice as fast as the rest of
it, then the maximum level of degradation should be:
Nmax=0.186*2Fal and
DPmin=800/ (0.186*2-Fal) +1 [27]
Assuming a variation of ±50% from the average, the range of degradation of

remaining winding insulation becomes:
N=0.5*(0.67/0.8)*(2-Fal/8.88)
And
DP=800/ (0.141*2-Fal+1) [27]
Another relationship which has been established is between the gases

produced during transformer operation and furfural production. It was found that at
temperatures in excess of 140˚C; insulating paper degradation contributes to the
production of hydrogen, methane, ethane and ethylene. But the most significant
relationship is between the paper and the production of carbon monoxide and carbon
dioxide. It was found that 50% of carbon dioxide is generated from the paper at
temperatures above 140°C [28]. There are different types of relations, like the
previous, even between the furans. From the five furfuraldehydes 2-Fal and 5-HMF
are the most important; they can be detected more easily due to their higher rates of
production. The major factor for the production of furan is temperature, but also the
factor that will determine the increase of production of them and therefore the
expected life time of the transformer. Dakin in 1948 showed that temperature is
related with chemical changes in the mechanism of paper degradation, and follows
Arrhenius equation. Later, he managed to develop an equation to predict the life-time
for a transformer [31]. The equation is:
t =A exp-E/RT= A exp-B/T [31]
24
where t is the time required for a specific property to decrease by a certain percentage
at a given temperature. A and B are constants, E is the activation energy, R is the gas
constant and T is the absolute temperature (° K) [31].
25
CHAPTER TWO
AIM, BACKGROUND
AND THE SCOPE
OF THE PROJECT
26
2.0 AIM, BACKGROUND AND THE SCOPE OF THE
PROJECT
Although there is significant evidence regarding how furans are produced

from the cellulosic insulating paper, the exact degradation mechanisms are not fully
understood [24]. It was mentioned above (section 1.4) the three possible causes of
paper degradation, but it is not known which of these three mechanisms is most likely
to occur on a transformer and which end products, with the exception of 2-FAL will
be produced. The intermediate steps involved are not known, and therefore which
other products may be produced. Furthermore, there is no knowledge regarding the
behaviour of the furans under different conditions. Furanic analysis is usefull for
monitoring the transformer and its operation, but specific knowledge relating to these
compounds is very poor. This project will investigate these compounds and examine
the furanic degradation process from a different perspective from that of previous
studies, which were mainly conducted with mineral oils [12, 13,16].
It is essential that such research be conducted due to a number of problems

with the current method of analysis. Furanic compounds are routinely analysed using
solid phase extraction (SPE) methods, in order to separate the furans from other
constituents such as carbonyl compounds, acids, followed by High Performance
Liquid Chromatography (HPLC) to achieve separation of the five selected furan
derivatives and also to be able to determine the concentrations of those furans present.
The method that is used is the industry standard IEC 61198 method, which, despite
being recognised worldwide, exhibits a number of problems:
The first problem arises from the sampling of the oil, which is
collected by the engineers for diagnostic analysis. Oil reclaimation,
vacuum degassing, are some influences that can affect the detection of
the furans, due to reduction in furan concentrations. The equilibrium
between oil and paper will be restored after a number of months of
operation, where furfural, primarily, will desorb from the paper into the
oil, but at a significantly lower concentration than in the untreated oil
[29].
27
Solid phase extraction, which is the next step of the analysis, plays a
crucial rule for the detection of furans. The sample is dissolved in
organic solvent in order to minimize the viscosity of the oil and then
passed through a silica cartridge, in order to achieve the adsorption,
hence entrapment of the polar compounds such as furans. A
significant issue is that the compounds are exposed to the environment
during this sample preparation step, and it is known from the literature
that air and moisture can affect the furans. The organic solvent might
affect the furans due to different properties and most importantly the
recovery of the furans from the silica might not be 100%.
The oxidising agents that can be present in the silica preparation can
affect the furans.
Several attempts have been made to establish an improved method for the
detection of furanic compounds in mineral oil. Apart from HPLC, researchers have
tried many different ways of analysing the samples and detecting the compounds,
notably by Infrared Spectroscopy, Gas Chromatography with Mass Spectrometric
detection, UV Spectroscopy [30]. Attempts to establish methods by which other
compounds can be determined, to give additional information as to the condition of a
transformer have been attempted.
However, before the investigation how these compounds can be detected it is

essential to try and understand how the compounds behave under different conditions,
such as temperature, pH and in the presence of organic matter. It is also essential to
examine the possibility that the oil itself can affect the furans and lead to the
production of other compounds than the furans in which with the current method they
are unable to be detected. The literature indicates that temperature can affect the
production and degradation of furanic compounds but in the examination of the aged
mineral oil [6]. Currently, there is no literature which details the basic mechanisms
by which furanic compounds react under the same conditions when they are in their
neat form and not in mineral oil.
28
Therefore the main aims of the project are:
To define a set of standard parameters under which furanic samples

will be prepared and to decide which analytical method is most suited
to the generation of reliable results with least interference problems.
To investigate the five furan derivatives in respect to key physical

properties, specifically stability and ageing, under the influence of
three primary process factors: temperature, pH and solvent.
To examine the furan degradation process and the production of other

derivatives.
To investigate the recovery and distribution of the furanic compounds

with clean mineral oils and how temperature affects this process.
Therefore, this project will examine each individual furan with the aim of
determining a number of factors governing compound formation and degradation, and
also to determine those parameters important with respect to the development and
improvement of the current industry standard method.
29
CHAPTER THREE
IDENTIFICATION OF FURANIC COMPOUNDS

&
CALIBRATION USING DIFFERENT
ANALYTICAL TECNIQUES
30
3.0 IDENTIFICATION OF FURANIC COMPOUNDS
AND CALIBRATION USING DIFFERENT
ANALYTICAL TECNIQUES
3.1 Aim
The aim of this chapter is to conduct an initial examination, in order to gain

some information regarding the furan compounds in order to establish:
The different analytical techniques that can be used for the

identification of furanic compounds. There is information in the
literature concerning these techniques, but only under limited
conditions [12, 14, and 30].
Which technique is most suited to proceed with the later experiments.
Calibration information for each furan derivative, by means of

determining the dynamic range of the analytical procedure. These
values will determine the standard solutions to be prepared and their
subsequent usage with respect to calibration of the instrument (HPLC,
UV-VIS, and Infrared).
3.2.0 Materials and Methods
3.2.1 General Materials
Below is a list with the materials used throughout this study. All materials
were obtained from Sigma-Aldrich:
Furfuryl alcohol 99%, Content: 50 g, Lot No: 09675-036, Cat. No:

18,593-0, b.p. 170 C, d 1.135
31
5-Methyl Furfural 99%, Content: 25 g, Lot No: 09517-027, Cat No:
13,731-6, b.p. 187 C, d. 1.107.
2-Acetyl Furfural 99%, Content: 25 g, Lot No: 12865-076, Cat No:

A1, 625-4, b.p. 67 C/10mm, d. 1.098.
5-Hydroxymethyl Furfural, Content: 5 g, Lot No: 11499-066, Cat No:

H4, 080-7, b.p. 114-116 C/1mm.
2-Furaldehyde 99%, Content: 25g, Lot No: 60712-018, Cat No:

18,591-4, b.p. 162 C, d. 1.160.
HPLC grade water, Content: 2.5L, Lot No: 60140, Cat No: 34877
Tetrachloroethylene 99%, Content: 2.5L, Lot No: 0273725, Cat No:

T/0600/17
3.2.2 Method for the Maximum Absorbance
Five solutions were prepared, one for each furan, by dissolving 0.2 g of the
material in 100 ml of HPLC grade water. The total concentration of each solution
was 0.2% w/v. Its solution was measured in a single UV-Visible spectrophotometer;
model Beckman DU640 (serial number 4319046), and the device was set for initial
scanning starting from 900 - 190 nm. The cell used for the analysis was quartz with 1
cm path length.
3.2.3 Calibration and Analysis Using HPLC, Infrared and

Fluorescence Spectroscopy Techniques
Once the maximum wavelength of absorbance was determined, a series of

solution were prepared containing 0.1 - 1000 ppm of furans in distilled water. A 1000
ppm stock solution was prepared, and was diluted to a lowest concentration of 0.1
32
ppm of furans. The dilutions were performed in a ratio 1:10, meaning that whenever a
lower dilution was performed it was not exceeding that ratio. The double beam UV-
Visible spectrophotometer measurements were performed at the specific maximum
absorbance, determined experimentally and varied according to the compound
analysed. Once again the cell used was a quartz cell with path length of 1 cm. table 2
and Figure 10 shows the results from the measurements and also the calibration
graphs, respectively, when UV-Vis spectroscopy analysis was used for that
determination.
The solutions that were prepared in Section 3.2.2 were also measured using a
fluorescent spectrometer. The instrument was set to scan from 150 - 900nm, with
excitation light wavelength set to the experimentally determined maximum
absorbance value for each derivative. The integration time was 0.1s with an
increment value of 1.0 cm. Figure 13 shows the resultant graphs obtained.
Another technique that was used to identify the furan compounds was Near
Infrared (NIR) Spectroscopy. For this type of analysis another set of solutions were
prepared by dissolving 0.2 g of each furan in 100 ml tetrachloroethylene to make up a
solution of 20 ppm. Furan-containing solutions were placed between two plates of
potassium bromide, which constituted the cell wall, and by setting the instrument for
scanning from 4000 - 400 cm-1. Figure 11 shows the graphs obtained from the
analysis.
Finally, another set of standard solutions were produced with concentrations in

the range of 0.025 ppm - 5 ppm. Solutions were prepared in water and analysed using
High Performance Liquid Chromatography. The instrument was set up according to
the specifications of the current IEC method for the analysis of furanic compounds.
The column that was used for the separation was a C-18 silica column with 25cm
length. The mobile phase of the isocratic gradient was a 15% acetonitrile in water and
70% acetonitrile in water. Two UV adsorption wavelengths were used for detection
purposes, 216 nm and 278 nm, since in those two wavelengths, according to the
standard method, all the five furan derivatives examined absorb light. Figure 12
shows the results.
33
3.3Results
3.3.1 Initial Scanning of Absorbance of furanic compounds

using UV-Vis spectroscopy
Below are the results for the five furan derivatives showing their UV absorbance
maxima when scanned across the range 900 nm - 190nm.
Table 1 Initial Scanning of the five furan derivatives using UV spectroscopy. The highlighted
numbers are indicating the wavelength that gives the highest absorbance.
Compound Wavelength Absorbance

in nm
194.5 3.1477
229 0.4426
5-HMF 268 3.7524
293 3.7844
296.5 3.7797
191.5 2.8887
226.5 0.4924
2-ACF 261 3.9148
286 3.7824
359 -0.0058
197 1.2238
205.5 3.6154
FOL 223 3.9258
886.5 -0.0086
889 -0.0086
193 3.0445
227.5 0.567
5-MEF 273.5 3.811
293 3.7844
307 3.7329
190.5 0.8117
229 0.6885
2-FAL 268.5 3.8472
284.5 3.7839
886 -0.0095
34
3.3.2 Calibration Results & Graphs of the five furans using
UV-Vis Spectroscopy.
The table below shows the results of a series of different concentrations of the
five furan derivatives measured using UV-Vis spectroscopy. The measurements were
performed according to the results from section 3.3.1, by reading each solution at its
maximum absorption. In the table below, are shown data used to create the
calibration graphs for each furan (Fig 12 a-e).
35
Table 2 Spectrophotometric response of the five furanic compounds in different concentrations at their maximum adsorption using UV spectroscopy.
5-HMF 2-ACF 5-MEF 2-FAL FOL

Concentration
of furanic Absorption Absorption Absorption Absorption Absorption
compounds in Corrected Corrected Corrected Corrected Corrected
ppm Abs Abs Abs Abs Abs
0 0.0535 0 0.261 0 0.0585 0 0.0369 0 0.0428 0
0.1 0.064 0.0105 0.2779 0.0169 0.13 0.0872
0.2 0.0758 0.0223 0.2887 0.0277 0.0631 0.0046 0.1438 0.101
0.5 0.1146 0.0611 0.3148 0.0538 0.0786 0.0201 0.0434 0.0065 0.1678 0.125
1 0.1653 0.1118 0.3556 0.0946 0.1034 0.0449 0.1558 0.1189 0.2114 0.1686
2 0.2781 0.2246 0.4808 0.2198 0.2178 0.1593 0.331 0.2941 0.29 0.2472
5 0.6245 0.571 0.9891 0.7281 0.3939 0.3354 0.6586 0.6217 0.5784 0.5356
10 1.1606 1.1071 1.2493 0.9883 0.9157 0.8572 1.6248 1.5879 0.9249 0.8821
50 3.3396 3.2861 2.0824 1.8214 3.109 3.0505 3.4367 3.3998 2.509 2.4662
100 3.4952 3.4417 2.137 1.876 3.4952 3.4367 3.4952 3.4583 2.5741 2.5313
200 3.613 3.5595 2.3404 2.0794 3.7377 3.6792 3.4367 3.3998 2.6775 2.6347
300 3.613 3.5595 2.3447 2.0837 3.7377 3.6792 3.613 3.5761 2.7268 2.684
400 3.613 3.5595 2.3447 2.0837 3.7377 3.6792 3.613 3.5761 2.9484 2.9056
500 3.613 3.5595 2.3551 2.0941 3.7377 3.6792 3.7377 3.7008 2.775 2.7322
1000 3.613 3.5595 2.407 2.146 3.9716 3.9131 3.9716 3.9347 2.9311 2.8883
36
Below are the calibration graphs of each individual furan showing also the
degree of linearity for each occasion. The maximum point from the linearity graph
will determine the initial concentration of each furan for later experiments.
CALIBRATION GRAPH OF 5-HMF AT 293nm
3.5
3
esponein293nm
2.5
2 LINEARITYPLOT OF5-HMF
R
1.2
1.5 1
0.8
0.6
y=0.1111x+0.0025
0.4
R2 =0.9998
1 0.2
0
0 5 10 15
0.5 CONC OF 5-HM F
0
0 20 40 60 80 100 120
Concentration of 5-HMF (ppm)
Fig 10 (a) Calibration graph of 5-HMF. The plot illustrates the concentration of each
solution versus the spectrophotometric response that the compound show at 293 nm
37
CALIBRATION GRAPF OF 5-MEF AT 273.5nm
3.5
3
.5nm
2.5
7
ein23
LINEARITY PLOT OF 5-MEF

s
2
n
o
1.5
esp
y=0.0871x- 0.017
R
R2 =0.9982
1.5 1
0.5
1
0
0.5 0 5 10 15
CONC OF 5-M EF
0
0 20 40 60 80 100 120
Concentration of 5-MEF (ppm)
Fig 10 (b) Calibration graph of 5-MEF. The plot illustrates the concentration of each
CALIBRATION GRAPH OF 2-ACF AT 203nm
2.5
2
m
LINEARITY PLOT OF2-ACF

0
ein23n
2
s
1.5
n
y =0.0991x +0.0093
po
1.5
s
R2 =0.9987
e
R
1
1
0.5
0
0.5 0 5 10 15
CONC OF 2-ACF
0
0 20 40 60 80 100 120
Concentration of 2-ACF (ppm)
Fig 10 (c) Calibration graph of 2-ACF. The plot illustrates the concentration of each
38
CALIBRATION OF 2-FAL AT 268.5nm
3.5
3 LINEARITY PLOT OF2-FAL

esponsein268.5nm
2.5 2
1.5 y=0.1637x- 0.0325

R2 =0.9975
2
1
1.5
R
0.5
1 0
0 5 10 15
CONC OF 2-FAL
0.5
0
0 20 40 60 80 100 120
Concentration of FAL (ppm)
Fig 10 (d) Calibration graph of 2-FAL. The plot illustrates the concentration of each
solution versus the spectrophotometric response that the compound show at 268.5 nm
CALIBRATION GRAPH OF FOL AT 223nm
2.5
LINERARITY PLOT OFFOL

esponsein223nm
2
2
1.5
1.5 y=0.0825x+0.0695
R2 =0.9897
1
R
1 0.5
0
0.5 0 5 10 15
CONC OF FOL
0
0 20 40 60 80 100 120
Concentration of FOL (ppm)
Fig 10 (e) Calibration graph of FOL. The plot illustrates the concentration of each
Figure 10 Calibration Graphs of the five furans by UV-Visible spectrophotometer. (a) 5-HMF,
(b) 5-MEF, (c) 2-ACF, (d) 2-FAL and (e) FOL.
39
3.3.3 Spectra of the five furanic compounds using Fourier
Transform Infrared Spectroscopy (FTIR).
FTIR spectroscopy is the absorption of electromagnetic radiation in the

-1
infrared region, which corresponds to 250 to 4000 cm (2.5 to 40 μm), of the
spectrum resulting in changes in the vibrational energy of molecules [32]. It was
mentioned above (see section 3.2.3) the method of preparing and analysing the
solutions by FTIR. The Figure (11) below shows the spectra obtained for each
individual furanic compound, approximately 20 ppm w/v in tetrachloroethylene, when
they were scanned from 400-4000 cm-1 wavenumber.
Fig 11 (a) Infrared Spectrum of 2-ACF in Tetrachroroethylene
40
Fig 11 (b) Infrared Spectrum of 2-FAL in Tetrachroroethylene
Fig 11 (c) Infrared Spectrum of FOL in Tetrachroroethylene.
41
Fig 11 (d) Infrared Spectrum of 5-HMF in Tetrachroroethylene
Fig 11 (e) Infrared Spectrum of 5-MEF in Tetrachroroethylene
Figure 11 Infrared Spectra of the five furans in Tetrachloroethylene solution. (a) 2-ACF, (b) 2-
FAL, (c) FOL, (d) 5-HMF and (e) 5-MEF
42
3.3.4 High Performance Liquid Chromatography results for
standard furan compounds analysed.
The table below shows the peak area obtained for each furan compound
performed in a series of different concentration solutions using HPLC analysis.
Table 3 Peak area results for the five furanic compounds of different concentration solutions
usingHPLC. The results obtained by identifying and integrating each peak from the spectrum to
determine the peak area of the appropriate furan.
CONCENTRATION
(ppm) AREA OF EACH FURAN
HMF FAL ACF MEF FOL
0 0 0 0 0 0
0.025 18525 9525 11539 6853 2498
0.05 36473 14373 17936 13890 4302
0.1 69492 22014 37246 27390 9618
0.5 339447 106312 198448 152600 43104
1 802902 219624 400284 320265 88343
2 1383786 541156 838544 659377 184952
5 3059593 1263765 2266884 1785384 643374
Figure 12 (a-e) shows the calibration graphs of each individual furanic

derivative by using the data presented above.
3500000
HMF
3000000
y = 616383x + 45387
2
R 0.9946 =
2500000
ABSORBANCE
2000000
1500000
1000000
500000
CONCENTRATION (ppm)
0
0.000 1.000 2.000 3.000 4.000 5.000 6.000
Fig 12 (a)Calibration graph of 5-HMF. The graph illustrates the concentration of each
solution measured versus the absorbance.
43
1400000
FAL
y = 254919x - 4332
2
1200000 R 0.998 =
1000000
800000
ABSORBANCE
600000
400000
200000
0
0 1 2 3
CONCENTRATION (ppm) 4 5 6
-200000
Fig 12 (b) Calibration graph of 2-FAL. The graph illustrates the concentration of
each solution measured versus the absorbance.
3000000
ACF
2500000
2000000
y = 451995x - 18772
R20.9988 =
1500000
ABSORBANCE
1000000
500000
0
0 1 2 3 4 5 6
CONCENTRATION (ppm)
-500000
Fig 12 (c) Calibration graph of 2-ACF. The graph illustrates the concentration of each
44
2000000
MEF
y = 356242x - 15580
1500000 R20.9989 =
1000000
ABSORBANCE
500000
0
0 1 2 3 4 5 6
CONCENTRATION (ppm)
-500000
Fig 12 (d) Calibration graph of 5-MEF. The graph illustrates the concentration of
each solution measured versus the absorbance.
800000.00
700000.00
FOL
600000.00
500000.00 y = 126550x - 15204

2
R 0.9859 =
ABSORBANCE
400000.00
300000.00
200000.00
100000.00
0.00 CONCENTRATION (ppm)

0 1 2 3 4 5 6
-100000.00
Fig 12 (e) Calibration graph of FOL. The graph illustrates the concentration of each
Figure 12 Calibration Graphs of the five furanic compounds by HPLC. (a) 5-HMF, (b) 2-FAL, (c)
2-ACF, (d) 5-MEF and (e) FOL
45
3.3.5 Results obtained for the five furanic compounds using
Fluorescence spectroscopy analysis.
Below are the spectra obtained for the five furanic compounds when they were
examined under fluorescence spectroscopy (see section 3.3.3 for the preparation
method). For each compound the maximum absorbance measured in previous section
(3.3.2) was used as the excitation wavelength. All the compounds were scan from
190 – 900 cm-1.
Fig 13 (a) fluorescent spectrum of 5-Hmf at 268 cm-1 excitation wavelength.
46
Fig 13(b) Fluorescent spectrum of 2-Fal at 268 cm-1 excitation wavelength.
Fig 13 (c) Fluorescent spectrum of 2-Acf at 286 cm-1 excitation wavelength.
47
Fig 13 (d) Fluorescent spectrum of 5-Mef at 273 cm-1 excitation wavelength.
Fig 13 (e) Fluorescent spectrum of Fol at 223 cm-1 excitation wavelength.
Figure 13 Fluorescent spectra of the five furanic compounds when they were scan from 190 –
900cm-1, each one at a different excitation wavelength.
48
3.4 Discussion
As was described in Section 3.1, this chapter was aimed at elucidating a

suitable approach with respect to the analytical techniques which can be used for the
identification, separation or even for the calibration of the furanic compounds. The
five furan derivatives were analysed using HPLC, UV-Vis spectroscopy, infrared
spectroscopy and fluorescence spectroscopy. The results from Section 3.3 shows that
furanic compounds can actually be identified using both spectroscopic and
chromatographic techniques.
Generally, the five furans were analysed in aqueous environments mainly for
two reasons. Firstly, water is a suitable solvent for the dissolution of the five furans
selected without the need for a co-solvent and secondly water exhibits less
interference with the methods selected. A significant issue was that water could not
be used as a solvent for the analysis of the furans by infrared spectroscopy. The
reason for that was the OH group from the water will interfere with the transmission
peaks obtained for the furan components. For that reason dichloethylene was used, a
compound that can dissolve all the furans exhibiting minimum interference effects in
the IR portion of the spectrum.
It was known from the IEC method that furans can be detected by HPLC and
UV-Vis spectroscopy. Literature indicates detection of furans using IR and
fluorescence spectroscopy when the compounds were extracted from mineral oil,
something that will be further discussed in this Section [30].
Section 3.3.1 reports the initial scanning experiments of each individual furan
in order to establish the maximum UV absorbance. It can be seen from Fig. 10 that
the maximum absorbance is different for each furan. The IEC method currently uses
two different UV detection wavelengths 278 nm and 216 nm to detect all the furans,
previously identified as the most suitable wavelength for furan detection. Because the
concentrations of the solutions prepared were based purely existing literature and
practical experience, a more precise indication of a maximum and minimum
49
detectable concentration was necessary. Such information is useful with respect to
determination of the solutions required for subsequent experimentation, with
particular applicability in selecting the starting concentrations for each furan with
respect to stability, ageing and degradation experiments. Fig 10 shows the graphs
produced when a series of different solutions were measured using UV-Vis
spectroscopy and using a fixed absorbance reading, according to the maximum
absorbance of each furan. It can be seen from the graphs (Fig 10) that the method
response becomes increasingly saturated for all the furan derivatives for
concentrations in excess of 30 ppm.
Blue et.al. [30] have used infrared spectroscopy to detect degradation of

insulating paper. It was found that there is a linear correspondence between the
furanic concentrations with infrared absorption. Also, it was found that the five
specific furan derivatives absorbs below 1700 cm-1, which agrees with the results
obtained in Section 3.3.3. Although, Blue et al. used different solvents and different
sample treatment protocols, the results are nevertheless comparable. Interpretation of
the spectra from Section 3.3.3 shows all the main constituents of the furan derivatives,
such as C-H bond adsorption at 2960 cm-1, alkenes at 3020 cm-1 and aromatics at
3026 cm-1. All these components also absorb also at lower regions such as 1400 cm-1
to 1600 cm-1. It may be noted that all the spectra exhibit some similarities, primarily
because all the furfuraldehydes examined are derivatives of the parent compound
furan.
Fluorescence spectroscopy was used also for the detection of furanic

compounds. From Figure 16, which illustrates the spectra obtained, it can be seen that
furanic compounds exhibit fluorescence at around 500 nm. For each furan derivative,
the excitation wavelength used was selected according to the maximum absorption
values from the previous experiment obtained in section 3.3.1. According to
literature, Blue et.al used fluorescence spectroscopy to detect FFA in mineral oil and
showed that at a range of 540 - 615 cm-1 wavelength a furan compounds excite light.
Once again, Blue and co-workers used different conditions and different
concentrations of FFA from those examined in this project, but with similar end-
results being obtained.
50
3.5 Conclusion
The work presented in this chapter has provided an initial approach with
respect to the selection and development of suitable analytical methods for the
determination of the selected furan derivatives. The five-furan derivatives were 5-
HMF, 2-FAL, 2-ACF, 5-MEF and FOL in which they were examined in their pure
form. Generally, this chapter investigated some of the properties of the furans, their
ability to react with other materials and an attempt has been made to correlate the
results of this project against existing literature.
In summary, this aspect of the study has examined the choice of solvent for
experiment, indicated useful optical properties for each individual furan, and
furthermore, provided information regarding potential methods for the analysis of the
derivatives via different analytical techniques.
It was shown that;
Water was a suitable solvent for the majority of studies potentially

exhibiting less interference effects when compared to the use of
organic solvents. This observation is of interest from the perspective
that later experiments may be performed in aqueous environments.
Each of the five furan derivatives has a different absorption value, but
all exhibit a maximum detection limit at around 30 ppm analyte.
All the furanic compounds can be analysed by HPLC, UV-Vis,

Infrared and fluorescence spectroscopy provided that the appropriate
conditions for detection are applied. Some of the techniques are more
sensitive than others, but due to the conditions that will be applied to
furan containing solutions, it was decided that UV-Vis and HPLC
techniques are the most appropriate for subsequent experiments.
51
Generally the results obtained from this chapter correlate with the
literature. It should be noticed that the conditions used for the
investigation in this project were completely different from the
condition of the literature, but the correlation was successful.
52
CHAPTER FOUR
AGEING, STABILITY &
DEGRADATION PRODUCTS
53
4.0 AGEING, STABILITY & DEGRADATION PRODUCTS
4.1 Aim
In this chapter, furanic compounds will undergo a series of different

experiments using two different analytical techniques to observe and to record the
changes happening to the compounds, during the ageing process. The furans will be
monitored frequently, for a period of time (approximately 2 months), to study the
behaviour of them under the influence of three parameters;
Temperature
pH
Alternative solvents.
(For further explanations of the choice of the conditions see section 4.4)
The results for these experiments will allow calculation of the rates of ageing
of each furan, their stability under the three imposed conditions, and the furanic
derivatives produced as a result of the degradation of each initial furan.
4.2 Materials and Methods
4.2.1 Materials
The furan derivatives which were used in this chapter were the same materials
used in section 3.2.1. In addition to those, the following materials, provided from
Sigma-Aldrich, were used;
Sodium Carbonate Anhydrous, Content: 2.5 Kg, Cat No: s/2840/62,
Lot No: 0119422.
Sodium Hydroxide, Content: 500g, Cat No: 102524X, Lot No:
B247450-306.
Potassium di-Hydrogen Phosphate 99.5%, Content: 250g, Cat No:
60221, Lot No: 1154873.
54
Sodium bicarbonate 99%, Content: 250g, Cat No: 88208, Lot No:
1137344.
Di-Sodium Hydrogen Phosphate Dihydrate 99%, Content: 250g, Cat
No: 71633, Lot No: 1157421.
Acetic Acid glacial, Content 2.5Lt, Cat No: A/0400/PB17, Lot No:
9911889-109
Methanol HPLC gradient grade, Content: 2.5Lt, Cat No: M/4058/17,
Lot No: 0397335.
Acetonitrile HPLC gradient grade, Content 2.5Lt, Cat No: 34851, Lot
No 53220.
4.2.2 Method
The ageing of furanic compounds against time was performed in three

different solvents, at four different temperatures and at three different pH values (see
table below).
Table 4 Illustration of the different conditions that the furanic compounds will be investigated for
the purpose of ageing, stability and degradation analysis.
SOLVENTS TEMPERATURE PH
FURANS IN AQUEOUS 0˚, 40˚, 60˚, 80˚ 4, 7, 11
SOLUTION
FURANS IN 0˚, 40˚, 60˚
ACETONITRILE
FURANS IN 0˚, 40˚, 60˚
METHANOL
Initially the furans were dissolved in water with a controlled pH i.e. the buffer
solution. Three different buffers were prepared for this experiment with ph 4.6, 6.8
and 10.
The buffer solution with pH 4.6 was produced by dissolving 10 g of Sodium

Hydroxide in 2.5 L of water. Slowly addition of 30 g of Acetic Acid was introduced
55
in order to decrease the pH and to stabilise at 4.6. For the buffer solution with pH 6.8
11.125 g of di-Sodium Hydrogen Phosphate were dissolved in water, 2.5Lt, and 8.5 g
of Potassium di-Hydrogen Phosphate was added to bring and to adjust the pH at 6.8.
Finally, for the last buffer, 5.25g of Sodium Carbonate was dissolved in water, 2.5 Lt,
and 6.625g of Sodium bicarbonate was used and dissolved to the solution in order to
fix the pH at 10. For all the pH measurements the instrument which was used was a
microprocessor pH meter from HANNA instruments, model pH 213, and purchased
from Sigma-Aldrich. Those buffer solutions were used as the solvent material for the
production of standard solutions, but also for the production of the samples which will
undergo the investigation.
For the construction of the standard solutions the same process was performed
as in section 3.2.3, and the concentrations of the standards were as follow; 5, 10, 20,
30, 40, and 50 ppm of furanic compounds. For the production of the samples each
furan was treated separately from each other by producing each sample at
concentration of 30 ppm at the three different pH values. The reason of producing
each furan at 30 ppm was the fact that; this was the point from the calibration at
section 3.2.3 where the linearity of the graph was tend towards a zero order response
profile. For each furan four identical solutions were produced in order that each one
of them to be stored at the four different temperatures (0, 40, 60 and 80˚C). Therefore
12 samples for each furan were produced. The standard solutions were kept at 0˚C in
order to minimize the degradation effect, and were used for the initial calibration
graph. The equation by the graph will be used for calculating the amount of
concentration which each furan is aged, but also is a way to observe and to monitor
the condition of the instrument.
Initially 5 ml of each sample from all the different conditions were taken out
from the place of storage and analysed using UV-Vis spectroscopy to obtain their
absorbance values at the specific wavelength according to the maximum limit of
detection for each individual species (see section 3.3.1).
Ageing of furanic compounds were also investigated in the presence of two

other solvents; acetonitrile and methanol. The only difference to the previous
experiment was that the sample consists of all the furan derivatives at 30 ppm each,
56
and the pH of the final solution was not controlled. Once again, a new set of standard
solutions was produced but this time in an organic solvent. In other words, a stock
solution of 1000 ppm of all the furans was produced by dissolving 0.5 g of each furan
in 500 ml of either Acetonitrile or Methanol. Dilutions were followed to produce the
standard solutions (concentrations of 1, 5, 10, 20, 30, 40 and 50 ppm) and the samples
at 30 ppm. Each sample was prepared in triplicate and stored at temperatures of 0, 40
and 60˚C. Another difference with the aqueous ageing investigation was that the
samples in organic matter were not stored at 80˚C, due to either close or above the
boiling point of the solvent. A 2 ml volume of sample was analysed using HPLC in
order to separate the furan species, and by using the peak area obtained from the
chromatograph, the furan concentration at that point in the aging process was
calculated. For the HPLC instrument the same conditions applied as in Section 3.2.3.
4.3 Results & Discussion
The experiments performed in this section illustrate how the ageing of furanic
compounds is well correlated with the stability that each individual furan shows
against specific parameters such as pH, temperature and under the influence of
different solvents.
Three different solvents were used; water, Acetonitrile and Methanol and the
choice of those specific solvents arise from the fact that those materials are used from
the existing method of either as solvent extractors of furans (the water) or as mobile
phase during the separation and the detection of those compounds using HPLC. The
choice of the pH was a general observation of the behaviour of furan in acidic (pH
4.6), neutral (pH 6.8) and basic (pH 10) environment. More precisely, the main
reason was to establish if the mineral insulating oil is under those conditions how it
can affect the stability and the detection of furans. Finally, the different temperatures
were chosen simply by the different temperatures that a transformer can operate
(normally between 50 to 70˚C) or according to the physical properties of the physical
properties of the solvent used for the investigation.
57
Initially the furanic compounds were examined individually in aqueous
environment under the different pH and temperatures described.
4.3.1 Ageing results in aqueous environment
Below are the results of the ageing experiment, when the furans, diluted in
water, where introduced into a specific and controlled environment, analysed over a
period of time using either UV-Vis spectroscopy or HPLC. Further below are the
graphs from the calibration of the standards but also the graphs from the results
obtained for each furan for the purposes of calculating the losses.
58
Table 5 Results from the calibration of the five furanic compounds under HPLC analysis
CALIBRATION OF 5-HMF CALIBRATION OF 2-FAL CALIBRATION OF 2-ACF CALIBRATION OF 5-MEF CALIBRATION OF FOL
ABS ABS ABS ABS ABS

CONC OF OF CORRECTED OF CORRECTED OF CORRECTED OF CORRECTED OF CORRECTED
FURANIC
COMPOUNDS ABS H2O ABS ABS H2O ABS ABS H2O ABS ABS H2O ABS ABS H2O ABS
0 0 0 0 0 0
5 0.638 0.0684 0.5696 0.769 0.1243 0.6447 0.473 0.046 0.4272 0.5002 0.0991 0.4011 0.494 0.16 0.334
10 1.288 0.0684 1.2196 1.408 0.1243 1.2837 0.923 0.046 0.8772 0.9184 0.0991 0.8193 0.828 0.16 0.668
20 2.162 0.0684 2.0936 2.533 0.1243 2.4087 1.768 0.046 1.7222 1.7066 0.0991 1.6075 1.422 0.16 1.262
30 2.972 0.0684 2.9036 3.261 0.1243 3.1367 2.518 0.046 2.4722 2.4509 0.0991 2.3518 1.787 0.16 1.627
40 3.312 0.0684 3.2436 3.354 0.1243 3.2297 2.966 0.046 2.9202 3.0531 0.0991 2.954 2.179 0.16 2.019
50 3.326 0.0684 3.2576 3.495 0.1243 3.3707 3.205 0.046 3.1592 3.286 0.0991 3.1869 2.261 0.16 2.101
59
STANDARD GRAPH OF 5-HMF
3.5
3
LINEARITY CURVE
2.5
ABS
3. 5
2 3
2. 5
1.5 1. 5
1
y = 0.0915x + 0.2095
0. 5 R 2 = 0.9923
0
1 0 5 10 15 20 25 30 35
CONC ( ppm)
0.5
0
0 10 20 30 40 50 60
CONCENTRATION (ppm)
Fig 14 (a) Standard graph of 5-HMF of different concentration solutions in aqueous

solution measured by HPLC.
STANDARD GRAPH OF 2-FAL
3.5
2.5 LINEARITY GRAPH

ABS
2 4
3
ABS
2
1.5 1
y = 0.1x + 0.243
0 R2 = 0.9866
1 0 5 10 15 20 25 30 35
CONC (ppm)
0.5
0
0 10 20 30 40 50 60
CONCNENTRATION (ppm)
Fig 14 (b) Standard graph of 2-FAL of different concentration solutions in aqueous

60
CALIBRATION GRAPH OF 2-ACF
3.5
2.5
LINEARITY GRAPH
2 3
ABS
2.5
2
1.5
ABS
1.5
y = 0.0828x + 0.0231
1
R2 = 0.9989
1 0.5
0
0 5 10 15 20 25 30 35
0.5 CONC (ppm )
0
0 10 20 30 40 50 60
CONCENRATION (ppm)
Fig 14 (c) Standard graph of 2-ACF of different concentration solutions in aqueous

STANDARD GRAPH FOR 5-MEF
3.5
2.5
LINEARITY CURVE
ABS
2 3
2.5 y = 0.0786x + 0.0146

2 R2 = 0.9996
1.5
ABS
1.5
1
0.5
1 0
0 5 10 15 20 25 30 35
0.5 CONC (ppm)
0
0 10 20 30 40 50 60
CONCENTRATION (ppm)
Fig 14 (d) Standard graph of 5-MEF of different concentration solutions in aqueous

61
STANDARD GRAPH OF FOL
2.5
LINEARITY GRAPH
1.5 1.8
1.6
ABS
1.4
1.2
ABS
1
1 0.8
y = 0.052x + 0.1279
0.6
0.4
R2 = 0.9843
0.2
0
0 5 10 15 20 25 30 35
0.5
CONC (ppm)
0
0 10 20 30 40 50 60
CONCENTRATION (ppm)
Fig 14 (e) Standard graph of FOL of different concentration solutions in aqueous

Figure 14 Calibration graphs of the five furanic compounds in water using UV-Vis spectroscopy;
(a) 5-HMF, (b) 2-FAL, (c) 2-ACF, (d) 5-MEF and (e) FOL.
The previous graphs show the calibration graphs for the five furanic
compounds. Below is a graphical representation of the ageing experiment for 5-HMF
under the different conditions applied and analysed for a period of 63 days. For a
detailed presentation of all the results obtained throughout that experiment see
appendix B.
62
AGEING OF 5-HMF AT PH4.6
35
30
25
CONC
20
15
5-HMFAT0 C
5-HMFAT40 C
10
5-HMFAT60 C
5-HMFAT80 C
5
0
0 7 14 21 28 35 42 49 56 63
DAYS
Fig15 (a) Ageing illustration of 5-HMF under different temperatures at a specific pH.
AGEING OF 5-HMF AT PH6.8
35
30
25
CONC
20
15
5-HMFAT0 C
10 5-HMFAT40 C
5-HMFAT60 C
5-HMFAT80 C
5
0
0 7 14 21 28 35 42 49 56 63
DAYS
Fig 15 (b) Ageing illustration of 5-HMF under different temperatures at a specific pH
63
AGEINGOF 5-HMF AT PH10
35
30
25
20
CONC
5-HMFAT0 C
15 5-HMFAT40 C
5-HMFAT60 C
10 5-HMFAT80 C
0
0 7 14 21 28 35 42 49 56 63
-5
DAYS
Fig 15 (c) Ageing illustration of 5-HMF under different temperatures at a specific pH
Figure 15 Ageing of 5-HMF at different pH under different temperatures.
Figure 15 illustrates the ageing examination of 5-HMF over 63 days and it can
be observed that at pH values of 4.6 and 6.8 that the compounds are stable at all
temperatures. Only in the case of pH 10 and at temperatures 60˚C and 80˚C the
compound shows signs of degradation. At 80˚C the degradation is immediate and
much steeper than the ageing at 60˚C, which has a much smoother decrease. It is
important to mention that the literature recommends that 5-HMF is the least stable
compound since its degradation, when the compound oxidised, produces other furan
derivatives, but according to the graphs provided in this investigation shows that 5-
HMF is fairly stable under those conditions( at least for pH 4.6 and 6.8).
Below is a graphical representation of the ageing experiment for 2-FAL under

the different conditions applied and analysed for a period of 63 days.
64
AGEINGOF 2-FAL ATPH4.6
35
30
25
20
CONC
15
10
2-FAL AT0 C
5 2-FAL AT40 C
2-FAL AT60 C
2-FAL AT80 C
0
0
14
21
28
35
42
49
56
63
DAYS
Fig 16 (a) Ageing illustration of 2-FAL under different temperatures at a specific pH
AGEINGOF 2-FAL ATPH6.8
35
30
25
20
CON C
15
10
2-FAL AT0 C
5 2-FAL AT40 C
2-FAL AT60 C
2-FAL AT80 C
0
0
14
21
28
35
42
49
56
63
DAYS
Fig 16 (b) Ageing illustration of 2-FAL under different temperatures at a specific pH
65
AGEINGOF 2-FAL ATPH10
35
30
25
20
2-FAL AT0 C
C ON C
2-FAL AT40 C
15
2-FAL AT60 C
2-FAL AT80
10
0
0
14
21
28
35
42
49
56
63
-5
DAYS
Fig 16 (c) Ageing illustration of 2-FAL under different temperatures at a specific pH

Figure 16 Ageing of 2-FAl at different pH under different temperatures
2-FAL in Figure 16 shows a different behaviour than the other furan

derivatives. At pH 4.6 and only at 60˚C shows ageing after 21 days. The same
profile follows at pH 6.8, but at pH 10 the degradation is much more obvious,
especially at 60 and 80˚C. After 10 days 2-FAL under that condition was not
observed.
Below is a graphical representation of the ageing experiment for 2-ACF under

66
AGEINGOF 2-ACF ATPH4.6
35
30
25
20
CONC
15
10
2-ACFAT0 C
5 2-ACFAT40 C
2-ACFAT60 C
2-ACFAT80 C
0
0
14
21
28
35
42
49
56
63
DAYS
Fig 17 (a) Ageing illustration of 2-ACF under different temperatures at a specific pH
AGEINGOF 2-ACF ATPH6.8
35
30
25
20
CONC
15
10
2-ACFAT0 C
2-ACFAT40 C
5
2-ACFAT60 C
2-ACFAT80 C
0
0
14
21
28
35
42
49
56
63
DAYS
Fig 17 (b) Ageing illustration of 2-ACF under different temperatures at a specific pH
67
AGEINGOF 2-ACF ATPH10
35
30
25
20
CONC
15
2-ACFAT0 C
2-ACFAT40 C
10
2-ACFAT60 C
2-ACFAT80 C
5
0
0
14
21
28
35
42
49
56
63
-5
DAYS
Fig 17 (c) Ageing illustration of 2-ACF under different temperatures at a specific pH

Figure 17 Ageing of 2-ACF at different pH under different temperatures.
2-ACF (Fig 17) behaves differently at the three pH values studied. Initially,
there is a small degradation at pH 4.6 and at 80˚C, but that profile changes at pH 6.8
when the solution stored at 0˚C shows the only sign of degradation. In the case of pH
10, once again 2-ACF follows the same pattern as 5-HMF and 2-FAL, with the only
difference that this compound needs 63 days to aged and not be detectable.
Below is a graphical representation of the ageing experiment for 5-MEF under

68
AGEINGOF 5-MEF ATPH4.6
35
30
25
20
CONC
15
10
5-MEFAT80 C
5-MEFAT60 C
5
5-MEFAT40 C
5-MEFAT0 C
0
0 7 14 21 28 35 42 49 56 63
DAYS
Fig 18 (a) Ageing illustration of 5-MEF under different temperatures at a specific pH
AGEINGOF5-MEFATPH6.8
35
30
25
CONC
20
15
5-MEFAT0 C
10
5-MEFAT40 C
5 5-MEFAT60 C
5-MEFAT80 C
0
0 7 14 21 28 35 42 49 56 63
DAYS
Fig 18 (b) Ageing illustration of 5-MEF under different temperatures at a specific pH
69
AGEINGOF 5-MEF ATPH10
35
30
25
20
CO NC
15 5-MEFAT0 C
5-MEFAT40 C
10 5-MEFAT60 C
5-MEFAT80 C
5
0
0 7 14 21 28 35 42 49 56 63
-5
DAYS
Fig 18 (c) Ageing illustration of 5-MEF under different temperatures at a specific pH

Figure 18 Ageing of 5-MEF at different pH under different temperatures.
When 5-MEF (Fig 18) was examined, the results showed that this furan
follows the same path of degradation as the furan 2-ACF, but only in the cases with
pH 6.8 and pH 10. When the furan was studied at pH 4.6 and at 0˚C, only then, there
were significant signs of degradation of about 6 ppm over the period of 63 days.
Below is a graphical representation of the ageing experiment for FOL under

70
AGEINGOF FOL ATPH4.6
35
FOL AT0 C
FOL AT40 C
30
FOL AT60 C
FOL AT80 C
25
20
CONC
15
10
0
0 7 14 21 28 35 42 49 56 63
-5
DAYS
Fig 19 (a) Ageing illustration of FOL under different temperatures at a specific pH
AGEINGOF FOL ATPH6.8
40
35
30
25
CONC
20
15
10 FOL AT0 C
FOL AT40 C
5 FOL AT60 C
FOL AT80 C
0
0 7 14 21 28 35 42 49 56 63
DAYS
Fig 19 (b) Ageing illustration of FOL under different temperatures at a specific pH
71
AGEINGOF FOL ATPH10
40
35
30
25
20
FOL AT0 C
CONC
15 FOL AT40 C
FOL AT60 C
10 FOL AT80 C
0
0 7 14 21 28 35 42 49 56 63
-5
-10
DAYS
Fig 19 (c) Ageing illustration of FOL under different temperatures at a specific pH

Figure 19 Ageing of FOL at different pH under different temperatures.
Figure 19 shows the examination of FOL for 63 days at the three different pH
and four different temperatures examined. It was noticed that FOL at pH 4.6 and at
all temperatures there was an instant loss of the compound, approximately by 20 ppm.
The instant loss was noticed as soon as the furanic compound was dissolved in that
particular buffer. At 0˚C there was a small increase of concentration over the period
of analysis, at 40˚C the compound remain stable, at 60˚C a gradual decrease and
finally, at 80˚C FOL was not detected after a period of 12 days. The initial and instant
decrease of the compound at pH 4.6 was a rapid reaction of the compound with the
buffer. It was noticed that if the pH of the solution was altered and changed from 4.6
to 6.8 after the initial measurement, the second reading will be the same as for the
initial reading of the solution prepared at buffer with pH 6.8. That means that FOL
under acidic environment shows sign of tautomerism between Keto-enol formations.
In other words FOL changes formation which is not able to be detected at that
specific wavelength. There is a possibility that at 0˚C the solution is trying to revert
back to its original keto structure and that is why that only a small increase of
concentration was observed. When FOL examined at pH 6.8 that instant loss of
72
concentration was detected, but at 0˚C there were signs of ageing. By looking at the
two graphs (Fig 19 a, b) it can be noticed that after 63 days of analysis the
concentration of FOL at 0˚C is the same in both cases. Finally, in the case of FOL
with buffer at pH 10 that spontaneous decrease of concentration also occurred, but
with less effect, and the ageing of the compound follows the same pattern as with the
other furan derivatives.
In that section it was showed the investigation of each individual furanic

compound in aqueous environment under different conditions. The graphical
representation shows how those conditions affect the concentration of the furanic
compounds over a period of 63 days.
4.3.2 Ageing results of the furanic compounds in acetonitrile and

methanol
The ageing process of the furan derivatives where also examined in an organic
environment. In that case the only difference to the previous study was the solvent
without altering the pH of the solutions. The study took place under three different
temperatures due to limitations of the solvents to high temperatures.
In this section are the results from the ageing experiment when the furanic
derivatives were dissolved in acetonitrile and methanol and analysed by HPLC.
Below are the results from the calibration with the graphs, which was used to retrieve
the values of the ageing of the furanic compounds. The results and the illustration of
the graphs are further below.
73
Table 6 Results of a series of different solutions used for the calibration of the furan derivatives
by HPLC.
CALIBRATION OF FURANS DISSOLVED IN ACETONITRILE USING HPLC

CONCENTRATION PEAK AREA
5-HMF 2-FAL 2-ACF 5-MEF FOL

0 0 0 0 0 0
1 30.1099 50.6088 40.6921 32.4741 25.4428
5 168.435 232.8 189.7 157 125.677
10 354.362 471.895 385.739 319.475 256.071
20 798.52 1030.52 845.1 699.82 560.5
30 1250 1598 1315 1189 1115
40 1907.74 2412.79 1997.72 1665.16 1364.4
50 2423.02 3120.92 2562.5 2137.32 1743.45
CALIBRATION OF FURANS DISSOLVED IN METHANOL USING HPLC

CONCENTRATION PEAK AREA
5-HMF 2-FAL 2-ACF 5-MEF FOL
0 0 0 0 0 0
1 45.5923 58.6989 47.337 38.4255 31.3075
5 229.553 289.369 232.928 195.299 157.356
10 420.886 529.909 428.212 364.212 290.262
20 910.426 1156.95 933.325 792.036 637.494
30 1193.6 1494.09 1212.51 1027.14 827.166
40 1493 1799.89 1463.7 1237.73 997.137
50 1956.82 2455.1 1997.71 1691.44 1361.86
74
STANDARD CURVE FOR 5-HMF IN ACETONITRILE
3000
2500
2000
PEAK AREA
1500
1000
y = 48.377x - 76.834
500
R2 = 0.9923
0
0 10 20 30 40 50 60
-500
CONCENTRATION
Fig 20 (a) Standard graph of 5-HMF of different concentration solutions in

acetonitrile measured by HPLC
STANDARD CURVE FOR 2-FAL IN ACETONITRILE
3500
3000
2500
PEAK AREA
2000
1500
1000
y = 61.654x - 87.57
500 R2 = 0.9922
0
0 10 20 30 40 50 60
-500
CONCENTRATION
Fig 20 (b) Standard graph of 2-FAL of different concentration solutions in acetonitrile

measured by HPLC
75
STANDARD CURVE FOR 2-ACF IN ACETONITRILE
3000
2500
2000
PEAK AREA
1500
1000
y = 50.794x - 73.421
500 R2 = 0.9922
0
0 10 20 30 40 50 60
-500
CONCENTRATION
Fig 20 (c) Standard graph of 2-ACF of different concentration solutions in acetonitrile

measured by HPLC
STANDARD CURVE FOR 5-MEF IN ACETONITRILE
2500
2000
1500
PEAK AREA
1000
y = 42.772x - 59.027
R2 = 0.9951
500
0
0 10 20 30 40 50 60
-500
CONCENTRATION
Fig 20 (d) Standard graph of 5-MEF of different concentration solutions in

acetonitrile measured by HPLC
76
STANDARD CURVE FOR FOL IN ACETONITRILE
2000
1500
PEAK AREA
1000
500
y = 35.591x - 45.203
R2 = 0.9917
0
0 10 20 30 40 50 60
-500
CONCENTRATION
Fig 20 (e) Standard graph of FOL of different concentration solutions in acetonitrile

measured by HPLC
Figure 20 Calibration graphs in Acetonitrile of (a) 5-HMF, (b) 2-FAL, (c) 2-ACF, (d) 5-MEF and
(e) FOL.
Below are the calibrations graphs of the five furanic compounds from a series
of different concentrations in methanol solution.
STANDARD CURVE FOR 5-HMF IN METHANOL
2500
2000
PEAK AREA
1500
1000
500
y = 38.288x + 34.621
R2 = 0.9946
0
0 10 20 30 40 50 60
CONCENTRATION
Fig 21 (a) Standard graph of 5-HMF of different concentration solutions in methanol

measured by HPLC
77
STANDARD CURVE FOR 2-FAL IN METHANOL
3000
2500
2000
PEAK AREA
1500
1000
y = 47.395x + 48.801
R2 = 0.9907
500
0
0 10 20 30 40 50 60
CONCENTRATION
Fig 21 (b) Standard graph of 2-FAL of different concentration solutions in methanol

measured by HPLC
STANDARD CURVE FOR 2-ACF IN METHANOL
2500
2000
PEAK AREA
1500
1000
500 y = 38.572x + 37.311

R2 = 0.9912
0
0 10 20 30 40 50 60
CONCENTRATION
Fig 21 (c) Standard graph of 2-ACF of different concentration solutions in methanol

measured by HPLC
78
STANDARD CURVE FOR 5-HMF IN METHANOL
2000
1800
1600
1400
PEAK AREA
1200
1000
800
600
y = 32.665x + 31.312
400 R2 = 0.9909
200
0
0 10 20 30 40 50 60
CONCENTRATION
Fig 21 (d) Standard graph of 5-MEF of different concentration solutions in methanol

measured by HPLC
STANDARD CURVE FOR FOL IN METHANOL
1600
1400
1200
PEAK AREA
1000
800
600
400 y = 26.314x + 24.702

R2 = 0.991
200
0
0 10 20 30 40 50 60
CONCENTRATION
Fig 21 (e) Standard graph of FOL of different concentration solutions in methanol

measured by HPLC
Figure 21 Calibration graphs in Methanol of (a) 5-HMF, (b) 2-FAL, (c) 2-ACF, (d) 5-MEF and
(e) FOL.
79
The table below shows the ageing results of 5-HMF in acetonitrile and
methanol solution measured for a period of 31 days of monitoring by HPLC.
Table 7 Results for the ageing of 5-HMF in Acetonitrile and Methanol.

5-HMF IN ACETONITRILE STORED AT O C 5-HMF IN ACETONITRILE STORED AT 4O C
PEAK CONCENTRATION PEAK CONCENTRATION

No OF DAYS OF No OF DAYS OF
AREA (ppm) AREA (ppm)
MEASUREMENT MEASUREMENT
1.00 1167.00 25.71 1.00 1203.00 26.46
3.00 929.10 20.79 3.00 1252.60 27.48
4.00 1154.00 25.44 4.00 1186.00 26.10
5.00 1173.00 25.84 5.00 1248.00 27.39
6.00 1402.00 30.57 6.00 1482.00 32.22
7.00 1178.00 25.94 7.00 1394.00 30.40
12.00 993.60 22.13 12.00 947.80 21.18
24.00 554.40 13.05 24.00 593.40 13.85
31.00 521.30 12.36 31.00 574.20 13.46
5-HMF IN ACETONITRILE STORED AT 6O C 5-HMF IN METHANOL STORED AT O C
PEAK CONCENTRATION
PEAK CONCENTRATION
No OF DAYS OF AREA (ppm) No OF DAYS OF
AREA (ppm)
MEASUREMENT MEASUREMENT
1.00 1252.00 27.47 1.00 1537.92 39.26
3.00 1489.00 32.37 3.00 1536.00 39.21
4.00 1186.00 26.10 4.00 1343.40 34.18
5.00 1234.00 27.10 5.00 1385.00 35.27
6.00 1206.00 26.52 6.00 1359.30 34.60
7.00 1161.00 25.59 7.00 1378.00 35.09
12.00 1191.00 26.21 12.00 1337.00 34.02
24.00 482.80 11.57 24.00 1489.00 37.99
31.00 496.30 11.85 31.00 1354.08 34.46
5-HMF IN METHANOL STORED AT 4O C 5-HMF IN METHANOL STORED AT 6O C
No OF DAYS OF PEAK No OF DAYS OF PEAK
CONCENTRATION CONCENTRATION
MEASUREMENT AREA MEASUREMENT AREA
1.00 1236.00 31.38 1.00 1228.00 31.17
3.00 1308.00 33.26 3.00 1385.00 35.27
4.00 1402.30 35.72 4.00 1376.30 35.04
5.00 1336.70 34.01 5.00 1030.30 26.00
6.00 986.64 24.86 6.00 1029.75 25.99
7.00 1171.20 29.68 7.00 1254.20 31.85
12.00 1310.00 33.31 12.00 1277.70 32.47
24.00 1216.50 30.87 24.00 983.90 24.79
31.00 1129.00 28.58 31.00 1033 26.08
80
Below is a graphical representation of the results from the ageing experiment
for 5-HMF in acetonitrile and methanol solutions and analysed for a period of 31
days.
5-HMF INACETONITRILE
35.00
5-HMFAT0 C
5-HMFAT40 C
30.00
5-HMFAT60 C
25.00
20.00
CONC
15.00
10.00
5.00
0.00
1.00 3.00 4.00 5.00 6.00 7.00 12.00 24.00 31.00
No OF DAYS
Fig 22 (a) Ageing illustration of 5-HMF in Acetonitrile solution under different

temperatures.
5-HMF INMETHANOL
45.00
40.00
35.00
30.00
25.00
CONC
20.00
15.00
10.00
5-HMFAT0 C
5.00 5-HMFAT40 C
5-HMFAT60 C
0.00
1.00 3.00 4.00 5.00 6.00 7.00 12.00 24.00 31.00
No OF DAYS
Fig 22 (b) Ageing illustration of 5-HMF in Methanol solution under different

temperatures.
Figure 22 Ageing progress of 5-HMF in (a) Acetonitrile and (b) Methanol over time.
81
Figure 22-26 shows the ageing results and the graphs obtained from that study.
Mainly, all the furan derivatives follow the same profile in all temperatures and at
both solvents. The only difference is with 5-HMF when treated in acetonitrile where
signs of degradation appears in all temperatures after the 12th day.
Overall, the furanic compounds in methanol are less stable compared to

acetonitrile, and the results obtained between 40˚C and 60˚C it can be seen that the
ageing at 40˚C is a day in delay from the ageing at 60˚C. At 0˚C the furan derivatives
in methanol shows great stability to their initial measurement, whereas in the case of
the acetonitrile the most stable results observed at 60˚C.
An assumption that can be made in the solutions in acetonitrile is that the

degradation of 5-HMF results in the production of the other furan derivatives, and
hence is a possible explanation as to the increase of 2-FAL, 2-ACF, 5-MEF and FOL,
especially at 40˚C. At 0˚C temperature, it can be seen that all the furanic compounds
at the 12th day they start to degradate but due to the loss of 5-HMF and maybe to the
production of other furans, the concentrations of the other furans increase and then
stabilize.
The final observation that was made was the increase of the concentration of
the solutions made in methanol. Initially all the samples were prepared to have a
starting concentration of 30 ppm, but the initial measurements shows an increase to
that value and only after the 5th day the concentration decreases to the proposed value.
This would suggest that there is a reaction between the furans with the methanol.
The table below shows the ageing results of 2-FAL in acetonitrile and
82
Table 8 Results for the ageing of 2-FAL in Acetonitrile and Methanol.
2-FAL IN ACETONITRILE STORED AT O C 2-FAL IN ACETONITRILE STORED AT 4O C

1.00 1466.00 25.20 1.00 1501.00 25.77
3.00 1179.80 20.56 3.00 1541.00 26.41
4.00 1465.00 25.18 4.00 1233.00 21.42
5.00 1488.00 25.56 5.00 1515.00 25.99
6.00 1785.00 30.37 6.00 1848.00 31.39
7.00 1495.00 25.67 7.00 1739.90 29.64
12.00 1208.00 21.01 12.00 1881.00 31.93
24.00 1521.40 26.10 24.00 1623.40 27.75
31.00 1485.00 25.51 31.00 1494.00 25.65
2-FAL IN ACETONITRILE STORED AT 6O C 2-FAL IN METHANOL STORED AT O C
1.00 1587.00 27.16 1.00 1886.00 38.76
3.00 1809.00 30.76 3.00 1836.20 37.71
4.00 1520.00 26.07 4.00 1513.00 30.89
5.00 1534.00 26.30 5.00 1518.00 31.00
6.00 1498.00 25.72 6.00 1474.40 30.08
7.00 1441.80 24.81 7.00 1616.40 33.08
12.00 1475.00 25.34 12.00 1579.00 32.29
24.00 1491.00 25.60 24.00 1609.00 32.92
31.00 1464.00 25.17 31.00 1647.07 33.72
2-FAL IN METHANOL STORED AT 4O C 2-FAL IN METHANOL STORED AT 6O C
1.00 1482.25 30.24 1.00 1470.00 29.99
3.00 1836.20 37.71 3.00 1504.70 30.72
4.00 1577.00 32.24 4.00 1454.00 29.65
5.00 1426.00 29.06 5.00 1117.00 22.54
6.00 986.60 19.79 6.00 1211.30 24.53
7.00 1385.00 28.19 7.00 1476.50 30.12
12.00 1519.60 31.03 12.00 1548.80 31.65
24.00 1482.00 30.24 24.00 1195.00 24.18
31.00 1294.70 26.29 31.00 1163.20 23.51
83
for 2-FAL in acetonitrile and methanol solutions and analysed for a period of 31 days.
2-FAL INACETONITRILE
35.00
30.00
25.00
20.00
CONC
15.00
10.00
2-FAL AT0 C
5.00
2-FAL AT40 C
2-FAL AT60 C
0.00
1.00 3.00 4.00 5.00 6.00 7.00 12.00 24.00 31.00
No OF DAYS
Fig 23 (a) Ageing illustration of 2-FAL in Acetonitrile solution under different

temperatures.
2-FAL INMETHANOL
40.00
35.00
30.00
25.00
CONC
20.00
15.00
10.00
2-FAL AT0 C
5.00 2-FAL AT40 C
2-FAL AT60 C
0.00
1.00 3.00 4.00 5.00 6.00 7.00 12.00 24.00 31.00
No OF DAYS
Fig 23 (b) Ageing illustration of 2-FAL in Methanol solution under different

temperatures.
Figure 23 Ageing progress of 2-FAL in (a) Acetonitrile and (b) Methanol over time
84
The table below shows the ageing results of 2-ACF in acetonitrile and
Table 9 Results for the ageing of 2-ACF in Acetonitrile and Methanol.

2-ACF IN ACETONITRILE STORED AT O C 2-ACF IN ACETONITRILE STORED AT 4O C
1.00 1210.66 25.28 1.00 1243.00 25.92
3.00 968.40 20.51 3.00 1280.00 26.65
4.00 1204.00 25.15 4.00 1233.00 25.72
5.00 1259.00 26.23 5.00 1266.00 26.37
6.00 1475.00 30.48 6.00 1544.00 31.84
7.00 1289.00 26.82 7.00 1445.50 29.90
12.00 1014.00 21.41 12.00 1580.00 32.55
24.00 1255.10 26.16 24.00 1344.00 27.91
31.00 1221.00 25.48 31.00 1237.90 25.82
2-ACF IN ACETONITRILE STORED AT 6O C 2-ACF IN METHANOL STORED AT O C

1.00 1307.00 27.18 1.00 1547.81 39.16
3.00 1497.30 30.92 3.00 1525.80 38.59
4.00 1253.30 26.12 4.00 1289.40 32.46
5.00 1273.00 26.51 5.00 1282.00 32.27
6.00 1245.90 25.97 6.00 1298.90 32.71
7.00 1194.20 24.96 7.00 1358.30 34.25
12.00 1226.80 25.60 12.00 1331.00 33.54
24.00 1245.60 25.97 24.00 1506.00 38.08
31.00 1493.60 30.85 31.00 1416.56 35.76
2-ACF IN METHANOL STORED AT 4O C 2-ACF IN METHANOL STORED AT 6O C

1.00 1224.86 30.79 1.00 1221.67 30.71
3.00 1241.30 31.21 3.00 1303.00 32.81
4.00 1344.20 33.88 4.00 1280.40 32.23
5.00 1228.90 30.89 5.00 966.30 24.08
6.00 938.80 23.37 6.00 1031.30 25.77
7.00 1177.00 29.55 7.00 1245.60 31.33
12.00 1292.00 32.53 12.00 1307.40 32.93
24.00 1235.70 31.07 24.00 1030.20 25.74
31.00 1050.00 26.25 31.00 961.10 23.95
85
for 2-ACF in acetonitrile and methanol solutions and analysed for a period of 31 days.
2-ACF IN ACETONITRILE
35.00
30.00
25.00
20.00
CONC
15.00
10.00
2-ACF AT 0 C
5.00 2-ACF AT 40 C
2-ACF AT 60 C
0.00
1.00 3.00 4.00 5.00 6.00 7.00 12.00 24.00 31.00
No OF DAYS
Fig 24 (a) Ageing illustration of 2-ACF in Acetonitrile solution under different

temperatures
2-ACF IN METHANOL
45.00
40.00
35.00
30.00
25.00
CONC
20.00
15.00
10.00
2-ACF AT 0 C
5.00 2-ACF AT 40 C
2-ACF AT 60 C
0.00
1.00 3.00 4.00 5.00 6.00 7.00 12.00 24.00 31.00
No OF DAYS
Fig 24 (b) Ageing illustration of 2-ACF in Methanol solution under different

temperatures
Figure 24 Ageing progress of 2-ACF in (a) Acetonitrile and (b) Methanol over time
86
The table below shows the ageing results of 5-MEF in acetonitrile and
Table 10 Results for the ageing of 5-MEF in Acetonitrile and Methanol.
5-MEF IN ACETONITRILE STORED AT O C 5-MEF IN ACETONITRILE STORED AT 4O C

1.00 1009.68 24.99 1.00 1034.79 25.57
3.00 808.30 20.28 3.00 1072.10 26.45
4.00 1001.00 24.78 4.00 1020.00 25.23
5.00 1098.00 27.05 5.00 1055.00 26.05
6.00 1241.60 30.41 6.00 1331.00 32.50
7.00 1023.40 25.31 7.00 1203.60 29.52
12.00 838.40 20.98 12.00 1312.00 32.05
24.00 1042.60 25.76 24.00 1111.90 27.38
31.00 1022.40 25.28 31.00 1034.80 25.57
5-MEF IN ACETONITRILE STORED AT 6O C 5-MEFIN METHANOL STORED AT O C
1.00 1088.04 26.82 1.00 1311.69 39.20
3.00 1251.50 30.64 3.00 1296.50 38.73
4.00 1045.50 25.82 4.00 1100.20 32.72
5.00 1024.00 25.32 5.00 1098.00 32.66
6.00 1055.00 26.05 6.00 1211.40 36.13
7.00 993.90 24.62 7.00 1154.10 34.37
12.00 1020.00 25.23 12.00 1138.00 33.88
24.00 1033.00 25.53 24.00 1271.30 37.96
31.00 1322.40 32.30 31.00 1169.57 34.85
5-MEF IN METHANOL STORED AT 4O C 5-MEF IN METHANOL STORED AT 6O C
1.00 1038.55 30.84 1.00 1031.25 30.61
3.00 1060.20 31.50 3.00 1116.10 33.21
4.00 1143.60 34.05 4.00 1098.40 32.67
5.00 1052.40 31.26 5.00 833.70 24.56
6.00 811.00 23.87 6.00 906.40 26.79
7.00 1051.70 31.24 7.00 1053.40 31.29
12.00 1092.70 32.49 12.00 1106.70 32.92
24.00 1035.30 30.74 24.00 920.90 27.23
31.00 889.00 26.26 31.00 803.10 23.63
87
for 5-MEF in acetonitrile and methanol solutions and analysed for a period of 31 days.
5-MEF IN ACETONITRILE
35.00
30.00
25.00
20.00
CONC
15.00
10.00
5.00 5- MEFAT 0 C
5- HMF AT 40 C
5- HMF AT 60 C
0.00
1.00 3.00 4.00 5.00 6.00 7.00 12.00 24.00 31.00
No OF DAYS
Fig 25 (a) Ageing illustration of 5-MEF in Acetonitrile solution under different

temperatures
5-MEF IN METHANOL
45.00
40.00
35.00
30.00
25.00
20.00
15.00
10.00
5-MEFAT 0C
5.00 5-MEFAT 40
5-MEFAT 60 C
0.00
1.00 3.00 4.00 5.00 6.00 7.00 12.00 24.00 31.00
No OF DAYS
Fig 25 (b) Ageing illustration of 5-MEF in Methanol solution under different

temperatures
Figure 25 Ageing progress of 5-MEF in (a) Acetonitrile and (b) Methanol over time.
88
The table below shows the ageing results of FOL in acetonitrile and methanol
solution measured for a period of 31 days of monitoring by HPLC.
Table 11 Results for the ageing of FOL in Acetonitrile and Methanol.

FOL IN ACETONITRILE STORED AT O C FOL IN ACETONITRILE STORED AT 4O C
1.00 830.36 24.60 1.00 846.05 25.04
3.00 697.60 20.87 3.00 927.80 27.34
4.00 813.54 24.13 4.00 829.51 24.58
5.00 861.30 25.47 5.00 899.20 26.53
6.00 1045.80 30.65 6.00 1093.40 31.99
7.00 863.40 25.53 7.00 1016.30 29.83
12.00 737.90 22.00 12.00 1142.20 33.36
24.00 883.60 26.10 24.00 955.90 28.13
31.00 857.80 25.37 31.00 879.00 25.97
FOL IN ACETONITRILE STORED AT 6O C FOL IN METHANOL STORED AT O C
1.00 878.82 25.96 1.00 1067.55 39.63
3.00 1056.20 30.95 3.00 1103.00 40.98
4.00 857.10 25.35 4.00 975.70 36.14
5.00 864.06 25.55 5.00 934.70 34.58
6.00 892.00 26.33 6.00 938.00 34.71
7.00 853.60 25.25 7.00 985.20 36.50
12.00 869.20 25.69 12.00 972.60 36.02
24.00 889.10 26.25 24.00 1075.00 39.91
31.00 1028.50 30.17 31.00 1040.00 38.58
FOL IN METHANOL STORED AT 4O C FOL IN METHANOL STORED AT 6O C
1.00 851.75 31.43 1.00 858.07 31.67
3.00 946.00 35.01 3.00 1005.00 37.25
4.00 1015.10 37.64 4.00 980.10 36.31
5.00 926.90 34.29 5.00 743.20 27.30
6.00 679.97 24.90 6.00 787.90 29.00
7.00 805.20 29.66 7.00 865.00 31.93
12.00 945.00 34.97 12.00 970.50 35.94
24.00 885.10 32.70 24.00 726.00 26.65
31.00 752.30 27.65 31.00 695.00 25.47
89
for FOL in acetonitrile and methanol solutions and analysed for a period of 31 days.
FOL IN ACETONITRILE
40.00
35.00
30.00
25.00
CONC
20.00
15.00
10.00
FOL AT 0 C
5.00 FOL AT 40 C
FOL AT 60 C
0.00
1.00 3.00 4.00 5.00 6.00 7.00 12.00 24.00 31.00
No OF DAYS
Fig 26 (a) Ageing illustration of FOL in Acetonitrile solution under different

temperatures
FOL IN METHANOL
45.00
40.00
35.00
30.00
25.00
CONC
20.00
15.00
10.00 FOL AT 0 C
5.00 FOL AT 40 C
FOL AT 60 C
0.00
1.00 3.00 4.00 5.00 6.00 7.00 12.00 24.00 31.00
No OF DAYS
Fig 26 (b) Ageing illustration of FOL in Acetonitrile solution under different

temperatures
Figure 26 Ageing progress of FOL in (a) Acetonitrile and (b) Methanol over time.
90
4.3 Results from the precipitation matter and the solutions at all pH at
60˚C and 80˚C.
An interesting observation for the solutions stored at 80˚C with pH 10 was the
formation of precipitation matter. That effect took place after the 7th day when the
solutions became cloudy and the precipitation process started. Although the pH of the
solutions was not changed significantly (from 10 to 11.2) that process indicates that a
reaction takes place between the furans and the buffer favouring the reaction towards
the formation of what may well be solid carbonate-based matter, since the original
compounds used for the buffer solution were sodium carbonate and sodium
bicarbonate. Therefore, the solution was filtered in order to collect the precipitate
matter for analysis by HPLC for the purpose of examining the possibility that other
furanic compounds were trapped during the precipitation process. Also, the
remaining solution was examined, alongside the other solutions at the other two pHs
tested, and finally all the solutions stored at 60˚C. The purpose of the experiment was
to investigate the possibility of formation of furan derivatives with a starting material
of a single furan. Table 12 shows the results obtained from that investigation and
show that;
During the formation of the precipitation matter at the solution with pH

10 stored at 80˚C the furan compound was trapped, possibly due to a
reaction with the buffer since from each individual furan, as a starting
material, formation of the other furans were detected, except of the
formation of FOL. However, FOL as the starting compound and after
a period of time can result in the production of the other four furanic
compounds.
It is possible from a single furan to produce other furan derivatives
under specific conditions.
Although, for that experiment HPLC analysis was used the results
agree with the results produced when the solutions were analysed with
UV-Vis spectroscopy.
91
Below are the results for the analysis of the precipitation matter that was
formed at all the solutions with pH10 stored at 80˚C. Also analysis of the solutions
were performed for those particular samples, and for the samples stored at 60˚C in
order to investigate any similarities or differences to that effect. For the calibration
graphs used to determine each value see appendix 2B.
92
Table 12 Results from the precipitation matter formed and also from the solutions filtered for each furan derivative in all pH at 60 C and 80 C using HPLC
STATE OF TEMPERAT PEAK AREA OF DETECTABLE FURANS/CONCENTRATION (ppm)
FURAN FURAN STORED PH 5-HMF 2-FAL 2-ACF 5-MEF FOL
AREA CONC AREA CONC AREA CONC AREA CONC AREA CONC
4.6 2819 34.42
SOLUTION 60 6.8 3143 38.28
10 23.9 1.19 9.2 0.96 26.7 0.41 58.2 1.50
5-HMF SOLUTION 4.6 4179 50.60
SOLUTION 80 6.8 1917.1 23.70
SOLUTION 10 16.9 1.11 38.7 1.37 92.5 1.23
PRECIPITA 10 15.7 1.09 18.4 1.09 53.3 0.74 76.2 1.77
4.6 2568 36.90
SOLUTION 60 6.8 2547 36.61
10 95.3 2.17 43.4 0.62
2-FAL SOLUTION 4.6 1513.8 22.09
SOLUTION 80 6.8 1635 23.80
SOLUTION 10 3.4 0.95 13.2 1.01 51.2 1.39
PRECIPITA 10 20.1 1.15 18.3 1.08 40.8 0.59 45.8 1.31
4.6 2713 33.84
SOLUTION 60 6.8 2374 29.62
10 6.4 0.98 15 1.04 2129 26.57
2-ACF SOLUTION 4.6 1433.7 17.92
SOLUTION 80 6.8 354.6 5.12 76.1 1.90 706.9 8.87
SOLUTION 10 59.3 1.61 51 1.54 87.2 1.93
PRECIPITA 10 19.6 1.14 13.4 1.02 14.7 0.26 10.7 0.78
93
Table 13 Results from the precipitation matter formed and also from the solutions filtered for each furan derivative in all pH at 60 C and 80 C using HPLC
TEMPERAT
STATE OF PEAK AREA OF DETECTABLE FURANS/CONCENTRATION (ppm)
URE
FURAN PH
FURAN STORED 5-HMF 2-FAL 2-ACF 5-MEF FOL
AREA CONC AREA CONC AREA CONC AREA CONC AREA CONC
4.6 7.9 0.94 1611.8 24.78

SOLUTION 60 6.8 4.4 0.89 1670 25.66
10 4.2 0.89 2.7 0.11 596.7 9.57
SOLUTION 4.6 11.9 0.99 1071.2 16.68
5-MEF
SOLUTION 6.8 5.1 0.97 5.8 0.91 1407 21.71
SOLUTION 80 10 33.9 1.31
PRECIPITA
10 1.1 0.92 16.6 1.06 36.3 0.53
TION
4.6 5.5 0.97 42.2 1.42 11 0.22 158 2.38
SOLUTION 60 6.8 1.3 0.92 20 1.11 24.1 0.38 2048 32.40
10 1.4 0.92 4.1 0.89 9.8 0.20 1729 27.33
SOLUTION 4.6 3.1 0.94 26.2 1.20 7.5 0.17
FOL 1.16790 1.13049
SOLUTION 6.8 21.5 21.2 1295.9 20.45
9 8
80
SOLUTION 10 1687 26.67
PRECIPITA
10 2.4 0.94 2.4 0.86 3.6 0.12
TION
94
4.4 Conclusion
In this chapter, furanic compounds were examined in different environments

under different conditions in order to observe parameters such as ageing, degradation
and production of furans and stability. The study showed that;
The ageing of furans depends upon the local environment.

Each furan shows different ageing sensitivity towards the conditions
used.
In aqueous environment with controlled pH, the furans are less stable
compared to furans in an organic environment.
Between the two organic environments examined the furans shows
greater stability in the acetonitrile rather than the methanol.
FOL degradate instantly in acidic environment due to tautomerism.
The other furanic compounds do not have that ability of changing
formation.
Degradation of a single furan results to the production of the other
furan derivatives.
General order of degradation from more to less, according to the
results, in aqueous environment of the furans is
2-FAL>5-HMF>FOL>2-ACF>5-MEF
Degradation of 5-HMF, 2-FAL, 2-ACF and 5-MEF does not result in
the formation of FOL but vice versa is possible.
95
CHAPTER FIVE
SUMMARY OF CONCLUSIONS &
FUTURE WORK
96
5.0 SUMMARY OF CONCLUSIONS AND FUTURE
WORK
The research work presented at this thesis investigates a series of different

properties that furanic compounds show. The specific furanic compounds analysed
are the products of the degradation process of the insulating cellulosic paper. It is
believed, according to the standard method IEC 6119, that 5-HMF, 2-FAL, 2-ACF, 5-
MEF and FOL are the main products of the degradation of the paper and investigation
of those compounds provide information relating to the state of the insulating paper.
This work presented the various techniques that are possible to use for the
analysis and detection of the furanic compounds, indicating also, by presenting
standard graphs, the amounts of furans which will be examined. It was established
that UV-Vis and HPLC were the two techniques which will be used for the
completion of the analysis of the furans.
The furanic compounds were examined under specific and controlled

environment, such as buffer solution at specific pH and temperature (chapter 4), to
determine the ageing, stability and degradation factors for the compounds. The
results showed that each furan behave differently from each other, depending to the
environment. In general, furans are less stable; degradate much faster in the aqueous
state than in an organic phase (Acetonitrile and Methanol). The pH of the
environment that the furans are located specify the rate of degradation, and in some
cases can act as a reagent by altering and changing the formation of the compound,
like in the case of FOL in acidic conditions where the compound showed signs of
tautomerism between the Keto-enol formation. Also, it is possible from one furan
derivative and after a period of degradation to produce other furan derivatives.
Obviously, the research work is an initial step of understanding the behaviour

of furanic compounds under different conditions.
97
Further work is needed to establish;
A kinetic model of the degradation of the furans. Basically the same

experiment of the ageing and stability must be repeated and from all
the results to try apply some kinetic parameters in order to explain the
rate of degradation.
Examination of ageing and stability of furans under different organic
environments, such as cyclohexane, dichlomethane, tetrahydrofuran, in
order to have a more general knowledge of the behaviour of furanic
compounds in organic matter.
Investigation of the maximum possible recovery of the furans that
favours the migration towards the oil.
Use of other extraction methods and matters, apart from silica cartridge
that the standard method recommends, to achieve maximum extraction
of furans and more stable, repeatable results.
The observations of the results from such investigation will provide valuable
information to improve the existing method for a better detection of the furanic
compounds and hence better knowledge of the insulating state of the transformer.
98
REFERENCES
99
REFERENCES
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and J. E. Triner, “Transformer Condition Monitoring-Realizing an Intergrated
Adaptive Analysis System”, CIGRE Paper No 12-105, 1992.
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Cellulosic Insulation in Power Transformers. Part 3: Effects of Oxygen and
Water on Ageing in Oil”, IEE Proc, Sci, Meas, Technol, Vol 147, No 3, 2000
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24) J.Scheirs, G.Camino, M.Avidano and W.Tumiatti, “Origin of Furanic
Compounds in Thermal Degradation of Cellulosic Insulating Paper” , 1998.
25) A.De Pablo and B. Pahlavanpour, “Furanic compounds analysis: a tool for
predictive maintenance of oil filled electrical equipment” 1997, p.175.
26) E. Serena “Degradation of transformers insulation” CIGRE, 1997.
27) A. De Pablo “Furfural and Ageing: How are they relate”, Asinel, Spain.
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Furfural Formation” IEEE, 2003.
101
29) Y.Shang, L.Yang, Z.J. Guo and Z.Yan, “Assessing Aging of Large
Transformers by Furfural Investigation”, IEEE Conf. on Solid Dielectrics,
2001, p.272.
30) R. Blue, D. Uttamchandani and O.Farish, “Infrared Detection of Transformer
Insulation Degradation Due to Accelerated Thermal Aging”, IEEE, Vol 5, No
2, 1998.
31) T. V. Oommen, T. A. Prevost, “Cellulose Insulation in Oil-Filled Power
Transformers: Part II – Maintaining Insulation Integrity and Life”, DEIS, Vol
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Chemistry”, Stanley Thornes (Publishers) Ltd, 4th Edition, 1999, p.377.
102
APPENDIX A
103
CHAPTER A
RECOVERY & DISTRIBUTION OF
FURANIC COMPOUNDS
104
A. RECOVERY & DISTRIBUTION OF FURANIC
COMPOUNDS
A.1 Aim
It is well known that furanic compounds are hydrophilic molecules, favouring

their presence towards aqueous environment, and therefore an examination of the
distribution of those compounds when they come in contact with other phases, e.g
mineral oil, was a necessity. Also, the recovery of the compounds from a matrix such
as oil will allow a determination of the amount that is recoverable as well as the loss.
It is essential to understand that in a transformer there is an exchange of furans
between the water residing in the insulating paper with the water residing in the
insulating oil. Hence, such an investigation will indicate the amount of furans that
prefer to stay in the water of the oil according to the distribution properties of the
compounds.
A.2 Materials and method
A.2.1 Materials
The materials used for that experiment were;
Water for gradient elution; Content: 2.5L, Lot No: 60140,

Cat No: 34877, provided from Sigma-Aldrich
Mineral insulating oil, provided from NYNAS Naphthenics Ltd.
A.2.2 Method
Initial solutions were prepared containing all the furanic compounds, each at
concentrations from 0.1 ppm to 50 ppm. Those solutions were used as standard
105
solutions as well as the samples which will be investigated. The process of
constructing those solutions is the same as in the case of section 3.2.3.
It was essential that the mineral insulating oil used, was saturated with water,
so that no further water would be absorbed when the sample was introduced into the
oil, which would later have lead to inaccuracies. Hence, 5 L of the oil was mixed
with 200ml of water, in order for the oil to become saturated; visible observation of
the free water in the oil used as the indicator of such saturation. 100ml of that oil was
mixed with 10 ml of the sample, each time with different concentration of the sample,
and stored for 30 minutes in an oven with 80˚C temperature. In total 8 samples were
stored, at varying furan concentrations. After 30 minutes that mixture was transferred
in a separating funnel to retrieve the aqueous phase. The remaining oil was washed
with another 10 ml of pure water and stored for another 30 minutes in the oven. Once
again, the aqueous phase was separated from the oil. The samples after the collection
were examined using HPLC in order to retrieve the data and to observe the changes
that occurred from the initial samples, i.e standards. In a further experiment the same
process was repeated with the only difference that this time the experiment took place
at 60˚C temperature. Also, the moisture content of the oil was recorded, before and
after the experiment, in order to study, how the temperature affects the oil and how
the different amounts of furanic compounds introduced into the oil can alter the
moisture of it.
A.3 Results
Below are the results obtained from the samples with different concentrations
at two different temperatures after two extractions when the samples where mixed
with clean mineral oil. The technique used for that investigation was HPLC analysis.
Extraction 1 is the amount of furan left in the water. Extraction 2 is the amount of
furan recovered from the oil.
106
First, recovery of 5-HMF.
Table 14 Recovery results for 5-HMF after two extractions indicating the total concentration
recovered with the percentage that corresponded to the extraction.
5-HMF TOTAL %
TEMPERATURE CONCENTRATION PEAK CONC CONC
RECOVERY
ºC (ppm) EXTRACTION AREA (ppm) (ppm)
1 0.01 0.36 360.38
0.1 0.91
2 14.70 0.55 553.45
1 27.70 0.72 144.85
0.5 1.16
2 5.40 0.43 86.25
1 12.90 0.53 52.98
1 0.96
2 5.33 0.43 43.03
1 316.43 4.52 90.35
5 5.25
2 28.50 0.73 14.70
60
1 567.10 7.81 78.11
10 9.39
2 92.50 1.58 15.76
1 1456.00 19.49 97.45
20 21.41
2 118.90 1.92 9.61
1 2398.80 31.88 106.26
30 35.96
2 283.40 4.08 13.61
1 3429.80 45.42 113.56
40 47.98
2 167.40 2.56 6.40
1 21.83 0.65 647.13
0.1 1.49
2 36.60 0.84 841.18
1 45.78 0.96 192.36
0.5 1.58
2 19.27 0.61 122.70
1 70.20 1.28 128.26
1 1.77
2 9.48 0.48 48.49
1 390.30 5.49 109.77
5 6.11
2 20.16 0.63 12.50
80
1 677.10 9.26 92.56
10 10.08
2 35.38 0.83 8.25
1 1559.00 20.84 104.22
20 22.12
2 69.49 1.27 6.37
1 2516.00 33.42 111.39
30 35.87
2 159.00 2.45 8.16
1 2633.00 34.95 87.39
40 39.23
2 297.90 4.27 10.69
107
Recovery of 2-FAL
Table 15 Recovery results for 2-FAL after two extractions indicating the total concentration
2-FAL TOTAL %
CONCENTRATION PEAK CONC CONC
RECOVERY
TEMPERATURE (ppm) EXTRACTION AREA (ppm) (ppm)
1 4.37 0.56 561.59
0.1 1.10
2 2.70 0.54 543.27
1 9.50 0.62 123.57
0.5 1.14
2 0.80 0.52 104.49
1 1.56 0.53 53.08
1 1.10
2 5.04 0.57 56.89
1 66.60 1.24 24.88
5 2.11
2 32.30 0.87 17.36
60
1 121.10 1.84 18.42
10 3.14
2 71.90 1.30 13.02
1 300.40 3.81 19.04
20 5.62
2 118.80 1.82 9.08
1 428.60 5.21 17.38
30 8.73
2 274.00 3.52 11.73
1 613.70 7.24 18.11
40 10.85
2 281.60 3.60 9.00
1 22.50 0.76 760.41
0.1 1.27
2 0.51 513.66
1 21.85 0.75 150.66
0.5 1.27
2 0.51 102.73
1 34.60 0.89 89.31
1 1.41
2 0.51 51.37
1 131.50 1.96 39.12
5 2.81
2 31.46 0.86 17.17
80
1 177.20 2.46 24.57
10 3.75
2 71.12 1.29 12.94
1 358.90 4.45 22.25
20 6.60
2 149.20 2.15 10.75
1 674.50 7.91 26.37
30 11.23
2 256.00 3.32 11.07
1 498.40 5.98 14.95
40 10.73
2 386.70 4.75 11.89
108
Recovery of 2-ACF
Table 16 Recovery results for 2-ACF after two extractions indicating the total concentration
2-ACF TOTAL %
RECOVERY
1 3.25 0.25 248.68
0.1 0.48
2 1.90 0.23 230.42
1 14.40 0.40 79.90
0.5 0.63
2 2.20 0.23 46.90
1 10.20 0.34 34.27
1 0.60
2 3.60 0.25 25.34
1 44.10 0.80 16.03
5 1.40
2 29.20 0.60 11.99
60
1 84.80 1.35 13.52
10 2.23
2 49.90 0.88 8.80
1 178.40 2.62 13.09
20 4.05
2 90.50 1.43 7.15
1 272.30 3.89 12.96
30 6.63
2 187.70 2.74 9.15
1 346.50 4.89 12.23
40 7.59
2 184.30 2.70 6.75
1 20.23 0.48 478.39
0.1 0.80
2 8.30 0.32 317.00
1 17.61 0.44 88.59
0.5 0.77
2 9.20 0.33 65.84
1 22.18 0.50 50.48
1 0.83
2 8.70 0.32 32.24
1 66.91 1.11 22.20
5 1.56
2 18.32 0.45 9.05
80
1 90.34 1.43 14.27
10 2.24
2 44.72 0.81 8.10
1 195.90 2.85 14.27
20 4.33
2 93.60 1.47 7.35
1 304.20 4.32 14.40
30 6.66
2 158.00 2.34 7.81
1 245.80 3.53 8.83
40 7.04
2 244.30 3.51 8.77
109
Recovery of 5-MEF
Table 17 Recovery results for 5-MEF after two extractions indicating the total concentration
5-MEF TOTAL %
RECOVERY
1 1.20 0.47 473.13
0.1 0.93
2 0.40 0.46 461.02
1 3.20 0.50 100.68
0.5 0.97
2 0.50 0.46 92.51
1 0.90 0.47 46.86
1 0.94
2 1.10 0.47 47.16
1 22.60 0.80 15.94
5 1.48
2 14.90 0.68 13.61
60
1 39.20 1.05 10.48
10 1.98
2 31.60 0.93 9.33
1 79.30 1.66 8.28
20 3.02
2 59.90 1.36 6.81
1 258.40 4.37 14.56
30 6.79
2 130.00 2.42 8.08
1 268.90 4.53 11.31
40 6.91
2 127.40 2.38 5.96
1 13.58 0.66 660.54
0.1 1.17
2 3.80 0.51 512.49
1 9.96 0.61 121.15
0.5 1.11
2 2.95 0.50 99.92
1 12.36 0.64 64.21
1 1.22
2 8.20 0.58 57.91
1 41.37 1.08 21.62
5 1.73
2 12.68 0.65 12.94
80
1 50.75 1.22 12.23
10 2.14
2 30.49 0.92 9.17
1 99.20 1.96 9.78
20 3.31
2 59.50 1.36 6.78
1 254.50 4.31 14.36
30 6.17
2 93.00 1.86 6.21
1 158.60 2.86 7.14
40 5.47
2 142.70 2.62 6.54
110
Recovery of FOL
Table 18 Recovery results for FOL after two extractions indicating the total concentration
FOL TOTAL %
RECOVERY
1 5.04 0.24 239.39
0.1 0.50
2 5.90 0.26 256.24
1 18.57 0.50 100.91
0.5 0.72
2 3.70 0.21 42.63
1 36.57 0.86 85.73
1 1.09
2 4.76 0.23 23.39
1 237.50 4.79 95.90
5 5.52
2 29.60 0.72 14.41
60
1 392.70 7.84 78.36
10 9.36
2 70.60 1.52 15.24
1 811.80 16.05 80.25
20 18.23
2 104.20 2.18 10.91
1 1161.80 22.91 76.36
30 27.99
2 252.00 5.08 16.93
1 1744.50 34.33 85.82
40 38.60
2 211.00 4.28 10.69
1 10.57 0.35 347.76
0.1 0.79
2 15.59 0.45 446.14
1 26.73 0.66 132.89
0.5 0.96
2 8.05 0.30 59.68
1 39.32 0.91 91.12
1 1.05
2 0.14 14.06
1 211.30 4.28 85.63
5 4.78
2 18.47 0.50 10.05
80
1 378.94 7.57 75.67
10 8.51
2 40.90 0.94 9.42
1 847.30 16.74 83.72
20 18.83
2 99.15 2.08 10.42
1 1363.90 26.87 89.56
30 27.01
2 0.14 0.47
1 1171.70 23.10 57.76
40 30.67
2 378.90 7.57 18.91
111
A.4 Discussion
As mentioned earlier, the insulation of a transformer mainly consists of

cellulosic paper and mineral oil. Unavoidably, both components contain a good
proportion, in different ratio, of water. When there is production of furanic
compounds in the paper due to breakdown of cellulosic insulating material, it is
believed that those compounds migrate from water molecules located in the paper to
water molecules in the oil, until they reach an equilibrium state dependent on
temperature. However, the ratio of that equilibrium state is not known. Although,
that migration process some amount of furans remain in the cellulosic paper.
With that experiment is an attempt of reconstructing the movement of furanic

compounds between a very hydrophilic phase, the paper, and a very hydrophobic
phase, the oil. The pure water acts as a model for the water located in the paper, and
when that water is mixed with the oil, which is already water-saturated (in order to
avoid any absorption of the water by the oil and hence the furanic compounds), will
give valuable information about how the furans are distributed in an oil water
environment, and give information about the amount of furans that is possible to
recover from an oil matrix.
Figure 38 shows the results for 5-HMF. It can be seen that this particular
compound can be recovered after the first extraction in both temperatures
investigated. That means that 5-HMF prefers the aqueous phase and there is no
distribution of the compound between the water and the oil. The problem arises when
it comes to the existing method where extraction of that compound comes from the
oil. If there is no movement of the compound from the paper to the oil there is no
detection of the compound and therefore no indication of the state of the degradation
of the cellulosic paper.
2-FAL analysis (see Fig 39) showed that this compound is not able to recover
the full amount even in the second extraction. Introducing more concentrated
solution, results to greater loss of the compound at the end of the measurement. The
112
interesting observation was that the compound behaves the same at both temperatures,
which means that this parameter does not affect of the migration and distribution of
the compound. Also, a higher concentration of that compound in to the oil means,
that ¾ of the initial concentration migrates to the oil. Only, up to 5 ppm is capable to
recover after the second extraction. Those results in comparison with the existing
method means, that although the compound distributed more towards the oil it is very
difficult to recover the actual amount that the oil contains of that furanic compound.
There is also, another possibility of that great loss, which is the degradation of the
compound due to the high temperature (60 and 80˚C). It was investigated earlier on,
the degradation of 2-FAL in aqueous controlled environment and showed that the
degradation is not immediate, at least not in the first hour, but in this case although the
environment is aqueous is different when is mixed with the oil, therefore the
parameters have changed and a relation factor is not possible.
Figure 40 and 41 shows the results for 2-ACF and 5-MEF respectively. Both
compounds behave the same as with the case of 2-FAL with the only difference that
2-ACF is not able to fully recovered for concentrations higher than 1 ppm.
Finally, FOL (see Fig 42) can be recovered fully from the first extraction at
60˚C, but in the case of the mixture treated at 80˚C temperature, the compound in the
highest concentration of 40 ppm was not been able to be fully recovered. Therefore,
there is a similar behaviour of FOL with 5-HMF.
Another explanation of why some of the furanic compounds prefer the

movement towards the oil is the fact that the moisture content of the oil increases.
Initially, the moisture content of the mineral oil was 4 ppm, after saturation the
moisture increases to 80 ppm. When the samples treated to the designated
temperatures the moisture from all the samples increased significantly to an extent of
280 ppm.
113
A.5 Conclusion
Furanic compounds are known as hydrophilic compounds moving through the

water molecules between the insulating cellulosic paper and the oil. That experiment
attempted to investigate and to explain that migration through the recovery process of
a known amount of furans, when they are located in an oil water environment. The
completion of the experiment showed that the furans are divided into two groups. The
first group include the compounds which show preference towards the aqueous
environment and there is no distribution of those compounds between the water and
the oil. Those compounds are found to be 5-HMF and FOL. The second group
involves the compounds that migrate and the majority of their presences prefer the oil.
Those compounds are 2-FAL, 2-ACF and 5-MEF. An important parameter for the
distribution of the furans and hence the migration of them from one state to the other,
is the moisture content of the oil. It was found that at 60 and 80˚C temperature the
moisture content of the oil increases to an extent that accelerates and attracts more
furanic compounds. However, that change of the moisture parameter seems to not
affect all the furans.
114
APPENDIX B
115
APPENDIX A TABLES OF AGEING RESULTS FOR THE FIVE FURAN DERIVATIVES AT DIFFERENT CONDITIONS FOR 63 DAYS
OF ANALYSIS.
Table 19 Ageing results for 5-HMF at pH 4.6 stored at 0 C for a period of 63 days Table 20 Ageing results for 5-HMF at pH 6.8 stored at 0 C for a period of 63
PH 4.6 PH 6.8
NO MEAN NO MEAN
DATE OF OF OF STANDARD ABS OF CORRECTED CONC DATE OF OF OF STANDARD ABS OF CORRECTED CONC
MEASUREMENT DAYS ABS DEVIATION BUFFER ABS PPM MEASUREMENT DAYS ABS DEVIATION BUFFER ABS PPM
0 30.00 0 30.00
31/07/2005 0 2.94 0.01 0.10 2.85 28.83 31/07/2005 0 2.94 0.02 0.09 2.85 28.88
01/08/2005 1 2.94 0.02 0.10 2.84 28.75 01/08/2005 1 3.03 0.04 0.10 2.93 29.74
02/08/2005 2 2.90 0.02 0.09 2.81 28.37 02/08/2005 2 3.00 0.01 0.09 2.91 29.52
03/08/2005 3 2.89 0.03 0.10 2.79 28.23 03/08/2005 3 2.95 0.02 0.10 2.84 28.80
04/08/2005 4 2.90 0.02 0.10 2.79 28.21 04/08/2005 4 2.96 0.03 0.11 2.85 28.86
05/08/2005 5 2.93 0.02 0.13 2.81 28.40 05/08/2005 5 2.96 0.01 0.12 2.84 28.74
06/08/2005 6 2.93 0.05 0.14 2.79 28.22 06/08/2005 6 2.97 0.02 0.13 2.84 28.78
07/08/2005 7 3.03 0.02 0.14 2.89 29.28 07/08/2005 7 3.03 0.04 0.14 2.89 29.33
10/08/2005 10 3.02 0.43 0.44 2.59 25.98 10/08/2005 10 3.24 0.03 0.43 2.81 28.40
13/08/2005 13 3.02 0.00 0.16 2.86 28.96 13/08/2005 13 3.01 0.03 0.15 2.85 28.89
16/08/2005 16 2.90 0.03 0.09 2.80 28.35 16/08/2005 16 2.92 0.03 0.09 2.83 28.64
19/08/2005 19 2.82 0.03 0.07 2.75 27.80 19/08/2005 19 2.86 0.03 0.07 2.79 28.24
22/08/2005 21 2.91 0.03 0.06 2.84 28.78 22/08/2005 21 2.86 0.03 0.07 2.80 28.28
30/08/2005 25 2.90 0.04 0.07 2.82 28.57 30/08/2005 25 2.90 0.03 0.08 2.82 28.51
06/09/2005 31 2.88 0.02 0.06 2.81 28.45 06/09/2005 31 2.94 0.02 0.07 2.87 29.07
09/10/2005 63 2.91 0.01 0.07 2.84 28.75 09/10/2005 63 2.90 0.02 0.16 2.73 27.57
of analysis. Days of analysis.
116
PH 10.0 PH 4.6
NO MEAN NO MEAN
0 30.00 0 30
31/07/2005 0 2.92 0.00 0.09 2.83 28.60 31/07/2005 0 2.94 0.01 0.10 2.85 28.83
01/08/2005 1 2.97 0.02 0.09 2.88 29.20 01/08/2005 1 2.98 0.04 0.10 2.88 29.22
02/08/2005 2 3.01 0.01 0.09 2.92 29.63 02/08/2005 2 2.99 0.02 0.09 2.90 29.41
03/08/2005 3 2.97 0.04 0.11 2.86 28.96 03/08/2005 3 2.99 0.03 0.10 2.88 29.24
04/08/2005 4 2.95 0.01 0.11 2.84 28.70 04/08/2005 4 2.96 0.02 0.10 2.85 28.90
05/08/2005 5 2.96 0.01 0.12 2.84 28.79 05/08/2005 5 2.97 0.01 0.12 2.86 28.94
06/08/2005 6 3.00 0.04 0.14 2.86 29.01 06/08/2005 6 2.97 0.01 0.13 2.84 28.73
07/08/2005 7 3.02 0.03 0.14 2.88 29.14 07/08/2005 7 3.08 0.06 0.13 2.95 29.94
10/08/2005 10 3.29 0.03 0.44 2.85 28.91 10/08/2005 10 3.28 0.04 0.42 2.86 28.96
13/08/2005 13 3.03 0.01 0.16 2.87 29.07 13/08/2005 13 3.02 0.02 0.15 2.87 29.09
16/08/2005 16 2.97 0.04 0.09 2.88 29.15 16/08/2005 16 2.96 0.05 0.08 2.88 29.20
19/08/2005 19 2.89 0.02 0.07 2.82 28.48 19/08/2005 19 2.92 0.02 0.06 2.86 29.01
22/08/2005 21 2.93 0.01 0.07 2.86 28.93 22/08/2005 21 2.91 0.02 0.05 2.85 28.90
30/08/2005 25 2.91 0.03 0.08 2.83 28.65 30/08/2005 25 2.92 0.01 0.05 2.87 29.07
06/09/2005 31 2.90 0.03 0.08 2.82 28.57 06/09/2005 31 2.94 0.03 0.05 2.88 29.20
09/10/2005 63 2.94 0.03 0.14 2.79 28.22 09/10/2005 63 2.93 0.02 0.08 2.86 28.93
Table 21 Ageing results for 5-HMF at pH 10 stored at 0 C for a period of 63 days Table 22 Ageing results for 5-HMF at pH 4.6 stored at 40 C for a period of 63
117
PH 6.8 PH 10.0
NO MEAN NO MEAN
0 30 0 30
31/07/2005 0 2.94 0.02 0.09 2.85 28.88 31/07/2005 0 2.92 0.00 0.09 2.83 28.60
01/08/2005 1 3.00 0.03 0.09 2.92 29.57 01/08/2005 1 2.96 0.02 0.09 2.86 29.01
02/08/2005 2 3.01 0.03 0.09 2.91 29.55 02/08/2005 2 2.96 0.01 0.10 2.86 28.99
03/08/2005 3 2.98 0.01 0.10 2.87 29.12 03/08/2005 3 2.98 0.03 0.11 2.87 29.10
04/08/2005 4 2.96 0.04 0.11 2.86 28.95 04/08/2005 4 2.95 0.03 0.11 2.84 28.75
05/08/2005 5 2.97 0.01 0.11 2.85 28.90 05/08/2005 5 2.96 0.02 0.12 2.84 28.78
06/08/2005 6 2.99 0.02 0.13 2.86 29.01 06/08/2005 6 3.00 0.03 0.14 2.86 29.00
07/08/2005 7 3.03 0.04 0.13 2.90 29.42 07/08/2005 7 2.95 0.01 0.14 2.81 28.46
10/08/2005 10 3.25 0.02 0.45 2.80 28.27 10/08/2005 10 3.24 0.02 0.44 2.80 28.33
13/08/2005 13 2.99 0.02 0.18 2.81 28.40 13/08/2005 13 2.96 0.03 0.16 2.81 28.37
16/08/2005 16 2.93 0.02 0.12 2.80 28.33 16/08/2005 16 2.87 0.03 0.10 2.78 28.05
19/08/2005 19 2.88 0.02 0.12 2.76 27.86 19/08/2005 19 2.83 0.02 0.08 2.75 27.79
22/08/2005 21 2.90 0.02 0.14 2.76 27.85 22/08/2005 21 2.80 0.03 0.08 2.73 27.52
30/08/2005 25 2.88 0.02 0.12 2.77 27.94 30/08/2005 25 2.77 0.02 0.08 2.69 27.10
06/09/2005 31 2.91 0.01 0.12 2.79 28.22 06/09/2005 31 2.72 0.02 0.08 2.64 26.53
09/10/2005 63 2.66 0.02 0.16 2.49 24.95 09/10/2005 63 2.57 0.01 0.11 2.47 24.69
Table 23 Ageing results for 5-HMF at pH 6.8 stored at 40 C for a period of 63 days Table 24 Ageing results for 5-HMF at pH 10 stored at 40 C for a period of 63
118
PH 4.6 PH 6.8
NO MEAN NO MEAN
0 30 0 30
31/07/2005 0 2.94 0.01 0.10 2.85 28.83 31/07/2005 0 2.94 0.02 0.09 2.85 28.88
01/08/2005 1 2.95 0.03 0.10 2.86 28.91 01/08/2005 1 2.98 0.03 0.09 2.90 29.37
02/08/2005 2 3.01 0.02 0.09 2.91 29.57 02/08/2005 2 2.99 0.02 0.10 2.89 29.28
03/08/2005 3 2.97 0.02 0.10 2.86 29.01 03/08/2005 3 2.96 0.05 0.10 2.85 28.91
04/08/2005 4 2.96 0.02 0.10 2.86 28.98 04/08/2005 4 2.95 0.02 0.10 2.85 28.82
05/08/2005 5 2.97 0.01 0.11 2.86 28.95 05/08/2005 5 2.95 0.01 0.11 2.84 28.75
06/08/2005 6 3.01 0.01 0.13 2.88 29.17 06/08/2005 6 2.97 0.01 0.13 2.84 28.77
07/08/2005 7 3.06 0.03 0.13 2.93 29.69 07/08/2005 7 3.02 0.02 0.13 2.89 29.28
10/08/2005 10 3.30 0.02 0.43 2.87 29.12 10/08/2005 10 3.25 0.03 0.43 2.82 28.57
13/08/2005 13 3.05 0.02 0.15 2.91 29.47 13/08/2005 13 2.96 0.03 0.15 2.82 28.48
16/08/2005 16 2.96 0.02 0.08 2.88 29.18 16/08/2005 16 2.92 0.01 0.08 2.84 28.71
19/08/2005 19 2.92 0.05 0.06 2.86 28.99 19/08/2005 19 2.87 0.03 0.06 2.81 28.44
22/08/2005 21 2.92 0.02 0.05 2.87 29.07 22/08/2005 21 2.88 0.02 0.05 2.83 28.59
30/08/2005 25 2.92 0.04 0.06 2.86 28.94 30/08/2005 25 2.90 0.04 0.06 2.84 28.73
06/09/2005 31 2.94 0.01 0.06 2.88 29.21 06/09/2005 31 2.90 0.02 0.06 2.84 28.75
09/10/2005 63 2.94 0.03 0.13 2.81 28.38 09/10/2005 63 2.84 0.02 0.08 2.76 27.85
Table 25 Ageing results for 5-HMF at pH 4.6 stored at 60 C for a period of 63 days Table 26 Ageing results for 5-HMF at pH 6.8 stored at 60 C for a period of 63
of analysis. days of analysis.
119
PH 10.0 PH 4.6
NO MEAN NO MEAN
0 30 0 30
31/07/2005 0 2.92 0.00 0.09 2.83 28.60 31/07/2005 0 2.94 0.01 0.10 2.85 28.83
01/08/2005 1 2.91 0.02 0.09 2.82 28.53 01/08/2005 1 3.06 0.05 0.10 2.96 30.08
02/08/2005 2 2.88 0.02 0.10 2.78 28.12 02/08/2005 2 3.00 0.02 0.10 2.91 29.47
03/08/2005 3 2.79 0.01 0.11 2.68 27.03 03/08/2005 3 2.96 0.02 0.11 2.85 28.88
04/08/2005 4 2.72 0.01 0.11 2.61 26.23 04/08/2005 4 2.97 0.02 0.11 2.86 28.94
05/08/2005 5 2.65 0.01 0.12 2.53 25.37 05/08/2005 5 2.97 0.01 0.12 2.85 28.83
06/08/2005 6 2.58 0.02 0.14 2.44 24.42 06/08/2005 6 3.01 0.03 0.15 2.86 28.95
07/08/2005 7 2.52 0.02 0.14 2.38 23.73 07/08/2005 7 3.07 0.05 0.15 2.92 29.65
10/08/2005 10 2.59 0.01 0.43 2.16 21.32 10/08/2005 10 3.29 0.01 0.47 2.82 28.57
13/08/2005 13 2.11 0.01 0.15 1.96 19.10 13/08/2005 13 2.99 0.03 0.20 2.79 28.20
16/08/2005 16 1.86 0.01 0.09 1.77 17.02 16/08/2005 16 2.96 0.03 0.14 2.82 28.54
19/08/2005 19 1.61 0.00 0.07 1.54 14.58 19/08/2005 19 2.93 0.03 0.13 2.80 28.36
22/08/2005 21 1.36 0.00 0.07 1.30 11.91 22/08/2005 21 2.91 0.02 0.14 2.77 27.93
30/08/2005 25 1.16 0.00 0.07 1.09 9.59 30/08/2005 25 2.96 0.02 0.18 2.77 28.03
06/09/2005 31 1.06 0.08 0.07 0.99 8.49 06/09/2005 31 2.96 0.03 0.18 2.78 28.06
09/10/2005 63 0.60 0.01 0.10 0.51 3.24 09/10/2005 63 2.94 0.02 0.08 2.86 28.96
Table 27 Ageing results for 5-HMF at pH 10 stored at 60 C for a period of 63 days Table 28 Ageing results for 5-HMF at pH 4.6 stored at 80 C for a period of
of analysis. 63 days of analysis.
120
PH 6.8 PH 10.0
NO MEAN NO MEAN
0 30 0 30
31/07/2005 0.00 2.94 0.02 0.09 2.85 28.88 31/07/2005 0 2.92 0.00 0.09 2.83 28.60
01/08/2005 1.00 2.98 0.03 0.09 2.89 29.30 01/08/2005 1 2.28 0.01 0.09 2.18 21.58
02/08/2005 2.00 3.00 0.02 0.13 2.87 29.11 02/08/2005 2 1.71 0.01 0.09 1.62 15.42
03/08/2005 3.00 2.98 0.03 0.12 2.86 28.98 03/08/2005 3 1.31 0.00 0.10 1.21 10.89
04/08/2005 4.00 2.95 0.03 0.12 2.83 28.66 04/08/2005 4 1.03 0.00 0.11 0.92 7.82
05/08/2005 5.00 2.96 0.01 0.13 2.83 28.68 05/08/2005 5 0.84 0.00 0.12 0.72 5.61
06/08/2005 6.00 2.98 0.02 0.14 2.84 28.71 06/08/2005 6 0.71 0.00 0.13 0.57 3.99
07/08/2005 7.00 3.06 0.06 0.15 2.91 29.50 07/08/2005 7 0.66 0.00 0.14 0.52 3.36
10/08/2005 10.00 3.22 0.04 0.44 2.78 28.08 10/08/2005 10 0.80 0.00 0.45 0.35 1.51
13/08/2005 13.00 2.97 0.02 0.16 2.81 28.38 13/08/2005 13 0.45 0.00 0.18 0.27 0.68
16/08/2005 16.00 2.91 0.01 0.09 2.82 28.52 16/08/2005 16 0.32 0.00 0.13 0.19 -0.16
19/08/2005 19.00 2.89 0.01 0.08 2.82 28.51 19/08/2005 19 0.30 0.00 0.13 0.17 -0.47
22/08/2005 21.00 2.90 0.03 0.07 2.84 28.70 22/08/2005 21 0.30 0.00 0.16 0.14 -0.75
30/08/2005 25.00 2.86 0.02 0.08 2.78 28.13 30/08/2005 25 0.32 0.01 0.18 0.14 -0.74
06/09/2005 31.00 2.88 0.01 0.08 2.79 28.25 06/09/2005 31 0.27 0.00 0.05 0.21 0.03
09/10/2005 63.00 2.81 0.01 0.10 2.71 27.32 09/10/2005 63 0.00 0.00 0.00 0.00 -2.29
Table 29 Ageing results for 5-HMF at pH 6.8 stored at 80 C for a period of 63 days Table 30 Ageing results for 5-HMF at pH 10 stored at 80 C for a period of 63
121
PH 4.6 PH 6.8
NO MEAN NO MEAN
0 30 0 30
01/08/2005 0 3.25 0.06 0.09 3.16 29.21 01/08/2005 0 3.20 0.01 0.10 3.10 28.57
02/08/2005 1 3.30 0.02 0.11 3.19 29.48 02/08/2005 1 3.24 0.02 0.11 3.13 28.87
03/08/2005 2 3.22 0.05 0.10 3.11 28.70 03/08/2005 2 3.24 0.00 0.11 3.13 28.85
04/08/2005 3 3.21 0.07 0.12 3.09 28.50 04/08/2005 3 3.21 0.05 0.13 3.08 28.42
05/08/2005 4 3.27 0.00 0.23 3.04 27.97 05/08/2005 4 3.26 0.03 0.14 3.12 28.81
06/08/2005 5 3.33 0.09 0.17 3.16 29.16 06/08/2005 5 3.34 0.02 0.16 3.19 29.43
07/08/2005 6 3.32 0.09 0.18 3.13 28.91 07/08/2005 6 3.27 0.06 0.17 3.10 28.57
08/08/2005 7 3.35 0.05 0.18 3.17 29.32 08/08/2005 7 3.32 0.06 0.17 3.14 28.99
12/08/2005 11 3.27 0.04 0.20 3.07 28.24 12/08/2005 11 3.19 0.02 0.18 3.01 27.70
15/08/2005 14 3.11 0.01 0.09 3.02 27.81 15/08/2005 14 3.15 0.05 0.09 3.06 28.15
18/08/2005 17 3.14 0.05 0.13 3.01 27.62 18/08/2005 17 3.13 0.02 0.13 3.00 27.54
23/08/2005 22 3.23 0.03 0.10 3.14 28.93 23/08/2005 22 3.20 0.04 0.09 3.11 28.69
08/09/2005 37 3.14 0.05 0.10 3.04 28.02 08/09/2005 37 3.14 0.05 0.10 3.04 27.98
09/10/2005 67 3.18 0.04 0.11 3.07 28.30 09/10/2005 67 3.11 0.04 0.18 2.93 26.86
Table 31 Ageing results for 2-FAL at pH 4.6 stored at 0 C for a period of 63 days Table 32 Ageing results for 2-FALat pH 6.8 stored at 0 C for a period of
of analysis. 63 days of analysis.
122
PH 10.0 PH 4.6
NO MEAN NO MEAN
0 30 0 30
01/08/2005 0 3.24 0.01 0.09 3.14 29.00 01/08/2005 0 3.25 0.06 0.09 3.16 29.21
02/08/2005 1 3.31 0.06 0.11 3.20 29.61 02/08/2005 1 3.30 0.06 0.10 3.20 29.55
03/08/2005 2 3.25 0.02 0.11 3.14 29.01 03/08/2005 2 3.23 0.06 0.10 3.13 28.91
04/08/2005 3 3.24 0.03 0.13 3.12 28.72 04/08/2005 3 3.25 0.06 0.12 3.13 28.89
05/08/2005 4 3.30 0.04 0.14 3.16 29.17 05/08/2005 4 3.32 0.02 0.14 3.18 29.35
06/08/2005 5 3.31 0.05 0.16 3.15 29.09 06/08/2005 5 3.33 0.07 0.15 3.18 29.41
07/08/2005 6 3.30 0.06 0.17 3.13 28.90 07/08/2005 6 3.36 0.06 0.16 3.20 29.56
08/08/2005 7 3.37 0.02 0.17 3.20 29.54 08/08/2005 7 3.32 0.05 0.16 3.16 29.19
12/08/2005 11 3.26 0.02 0.19 3.07 28.30 12/08/2005 11 3.29 0.05 0.17 3.12 28.75
15/08/2005 14 3.20 0.06 0.09 3.11 28.70 15/08/2005 14 3.19 0.05 0.07 3.12 28.79
18/08/2005 17 3.16 0.03 0.12 3.04 27.96 18/08/2005 17 3.14 0.04 0.10 3.04 27.95
23/08/2005 22 3.23 0.06 0.08 3.14 28.98 23/08/2005 22 3.23 0.03 0.07 3.17 29.22
08/09/2005 37 3.13 0.02 0.09 3.04 27.95 08/09/2005 37 3.12 0.03 0.07 3.05 28.02
09/10/2005 67 3.18 0.05 0.16 3.03 27.84 09/10/2005 67 3.23 0.02 0.09 3.14 28.98
Table 33 Ageing results for 2-FAL at pH 10 stored at 0 C for a period of 63 days Table 34 Ageing results for 2-FAL at pH 4.6 stored at 40 C for a period of 63
123
PH 6.8 PH 10.0
NO MEAN NO MEAN
0 30 0 30
01/08/2005 0 3.20 0.01 0.10 3.10 28.57 01/08/2005 0 3.24 0.01 0.09 3.14 29.00
02/08/2005 1 3.26 0.04 0.11 3.15 29.12 02/08/2005 1 3.33 0.05 0.11 3.22 29.78
03/08/2005 2 3.29 0.05 0.10 3.18 29.39 03/08/2005 2 3.22 0.05 0.11 3.12 28.73
04/08/2005 3 3.20 0.04 0.12 3.09 28.42 04/08/2005 3 3.24 0.04 0.13 3.11 28.67
05/08/2005 4 3.28 0.05 0.14 3.15 29.04 05/08/2005 4 3.29 0.03 0.14 3.15 29.11
06/08/2005 5 3.36 0.07 0.15 3.22 29.75 06/08/2005 5 3.31 0.05 0.15 3.15 29.11
07/08/2005 6 3.28 0.06 0.16 3.12 28.80 07/08/2005 6 3.27 0.03 0.17 3.11 28.64
08/08/2005 7 3.31 0.04 0.17 3.15 29.02 08/08/2005 7 3.30 0.04 0.17 3.13 28.86
12/08/2005 11 3.23 0.02 0.21 3.02 27.77 12/08/2005 11 3.27 0.06 0.19 3.08 28.33
15/08/2005 14 3.17 0.05 0.12 3.04 28.01 15/08/2005 14 3.17 0.05 0.10 3.07 28.28
18/08/2005 17 3.12 0.06 0.16 2.96 27.17 18/08/2005 17 3.16 0.01 0.14 3.02 27.80
23/08/2005 22 3.21 0.03 0.14 3.08 28.36 23/08/2005 22 3.22 0.02 0.09 3.13 28.85
08/09/2005 37 3.12 0.03 0.16 2.96 27.18 08/09/2005 37 3.09 0.05 0.10 2.99 27.44
09/10/2005 67 3.20 0.01 0.20 3.00 27.57 09/10/2005 67 3.12 0.02 0.11 3.01 27.69
Table 35 Ageing results for 2-FAL at pH 6.8 stored at 40 C for a period of 63 days Table 36 Ageing results for 2-FAL at pH 10 stored at 40 C for a period of 63
124
PH 4.6 PH 6.8
NO MEAN NO MEAN
0 30 0 30
01/08/2005 0 3.25 0.06 0.09 3.16 29.21 01/08/2005 0 3.20 0.01 0.10 3.10 28.57
02/08/2005 1 3.30 0.06 0.11 3.19 29.50 02/08/2005 1 3.31 0.04 0.11 3.20 29.61
03/08/2005 2 3.25 0.02 0.11 3.14 28.96 03/08/2005 2 3.24 0.05 0.11 3.14 28.93
04/08/2005 3 3.23 0.01 0.12 3.11 28.66 04/08/2005 3 3.24 0.07 0.12 3.11 28.71
05/08/2005 4 3.28 0.05 0.13 3.15 29.08 05/08/2005 4 3.28 0.02 0.13 3.15 29.06
06/08/2005 5 3.34 0.05 0.14 3.20 29.52 06/08/2005 5 3.26 0.04 0.15 3.12 28.75
07/08/2005 6 3.35 0.07 0.16 3.19 29.47 07/08/2005 6 3.29 0.05 0.16 3.13 28.89
08/08/2005 7 3.30 0.07 0.16 3.14 28.93 08/08/2005 7 3.27 0.07 0.16 3.11 28.67
12/08/2005 11 3.27 0.04 0.17 3.10 28.60 12/08/2005 11 3.26 0.07 0.17 3.09 28.43
15/08/2005 14 3.17 0.03 0.07 3.09 28.49 15/08/2005 14 3.14 0.04 0.08 3.06 28.20
18/08/2005 17 3.17 0.04 0.10 3.07 28.22 18/08/2005 17 3.09 0.03 0.11 2.98 27.40
23/08/2005 22 3.26 0.06 0.07 3.19 29.46 23/08/2005 22 3.19 0.06 0.07 3.12 28.73
08/09/2005 37 2.46 0.01 0.09 2.37 21.30 08/09/2005 37 2.38 0.01 0.08 2.31 20.64
09/10/2005 67 2.21 0.03 0.16 2.05 18.05 09/10/2005 67 2.19 0.04 0.09 2.10 18.54
Table 37 Ageing results for 2-FAL at pH 4.6 stored at 60 C for a period of 63 days Table 38 Ageing results for 2-FAL at pH 6.8 stored at 60 C for a period of 63
125
PH 10.0 PH 4.6
NO MEAN NO MEAN
0 30 0 30
01/08/2005 0 3.24 0.01 0.09 3.14 29.00 01/08/2005 0 3.25 0.06 0.09 3.16 29.21
02/08/2005 1 3.29 0.07 0.11 3.18 29.39 02/08/2005 1 3.35 0.03 0.10 3.25 30.04
03/08/2005 2 3.24 0.05 0.11 3.12 28.80 03/08/2005 2 3.25 0.06 0.12 3.13 28.88
04/08/2005 3 3.19 0.04 0.12 3.07 28.24 04/08/2005 3 3.27 0.03 0.14 3.13 28.86
05/08/2005 4 3.23 0.03 0.14 3.09 28.46 05/08/2005 4 3.30 0.08 0.15 3.15 29.09
06/08/2005 5 3.23 0.06 0.15 3.08 28.34 06/08/2005 5 3.34 0.02 0.18 3.17 29.24
07/08/2005 6 3.17 0.06 0.16 3.00 27.61 07/08/2005 6 3.34 0.03 0.19 3.15 29.08
08/08/2005 7 3.14 0.03 0.17 2.97 27.32 08/08/2005 7 3.36 0.09 0.23 3.14 28.95
12/08/2005 11 2.85 0.02 0.18 2.67 24.30 12/08/2005 11 3.26 0.06 0.25 3.01 27.71
15/08/2005 14 2.49 0.01 0.08 2.41 21.66 15/08/2005 14 3.12 0.04 0.16 2.96 27.18
18/08/2005 17 2.28 0.01 0.12 2.16 19.20 18/08/2005 17 3.13 0.03 0.33 2.79 25.50
23/08/2005 22 1.96 0.01 0.08 1.87 16.31 23/08/2005 22 3.23 0.06 0.20 3.04 27.95
08/09/2005 37 0.72 0.00 0.09 0.63 3.88 08/09/2005 37 3.09 0.05 0.20 2.90 26.55
09/10/2005 67 0.74 0.00 0.13 0.60 3.61 09/10/2005 67 3.03 0.04 0.19 2.85 26.05
Table 39 Ageing results for 2-FAL at pH 10 stored at 60 C for a period of 63 days Table 40 Ageing results for 2-FAL at pH 4.6 stored at 80 C for a period of 63
126
PH 6.8 PH 10.0
NO MEAN NO MEAN
0 30 0 30
01/08/2005 0 3.20 0.01 0.10 3.10 28.57 01/08/2005 0 3.24 0.01 0.09 3.14 29.00
02/08/2005 1 3.29 0.05 0.15 3.15 29.05 02/08/2005 1 2.97 0.01 0.12 2.85 26.03
03/08/2005 2 3.24 0.04 0.12 3.12 28.80 03/08/2005 2 2.28 0.01 0.11 2.17 19.23
04/08/2005 3 3.20 0.03 0.13 3.07 28.27 04/08/2005 3 1.79 0.01 0.13 1.66 14.13
05/08/2005 4 3.27 0.00 0.15 3.13 28.83 05/08/2005 4 1.28 0.00 0.15 1.13 8.85
06/08/2005 5 3.29 0.04 0.16 3.13 28.83 06/08/2005 5 1.00 0.00 0.16 0.83 5.91
07/08/2005 6 3.24 0.04 0.17 3.07 28.28 07/08/2005 6 0.85 0.00 0.18 0.68 4.36
08/08/2005 7 3.29 0.03 0.18 3.11 28.67 08/08/2005 7 0.76 0.00 0.19 0.57 3.23
12/08/2005 11 3.19 0.03 0.19 3.00 27.60 12/08/2005 11 0.52 0.00 0.24 0.28 0.38
15/08/2005 14 3.15 0.04 0.09 3.05 28.09 15/08/2005 14 0.37 0.00 0.18 0.19 -0.54
18/08/2005 17 3.12 0.03 0.14 2.98 27.38 18/08/2005 17 0.30 0.00 0.24 0.07 -1.78
23/08/2005 22 3.23 0.05 0.09 3.13 28.92 23/08/2005 22 0.44 0.00 0.29 0.15 -0.97
08/09/2005 37 3.08 0.02 0.10 2.98 27.37 08/09/2005 37 0.31 0.00 0.06 0.24 0.00
09/10/2005 67 3.07 0.04 0.11 2.96 27.13 09/10/2005 67 0.00 0.00 0.00 0.00 0.00
Table 41 Ageing results for 2-FAL at pH 6.8 stored at 80 C for a period of 63 days Table 42 Ageing results for 2-FAL at pH 10 stored at 80 C for a period of 63
of analysis days of analysis.
127
PH 4.6 PH 6.8
NO MEAN NO MEAN
0 30 0 30
01/08/2005 0 2.43 0.02 0.05 2.38 28.42 01/08/2005 0 2.42 0.02 0.05 2.38 28.42
02/08/2005 1 2.41 0.02 0.13 2.28 27.32 02/08/2005 1 2.42 0.01 0.12 2.30 27.50
03/08/2005 2 2.40 0.01 0.09 2.32 27.69 03/08/2005 2 2.39 0.02 0.09 2.31 27.60
04/08/2005 3 2.52 0.02 0.15 2.36 28.25 04/08/2005 3 2.54 0.01 0.14 2.40 28.75
05/08/2005 4 2.44 0.02 0.17 2.28 27.21 05/08/2005 4 2.54 0.02 0.15 2.39 28.63
06/08/2005 5 2.47 0.03 0.17 2.30 27.50 06/08/2005 5 2.55 0.02 0.16 2.39 28.62
07/08/2005 6 2.47 0.02 0.18 2.30 27.45 07/08/2005 6 2.55 0.01 0.17 2.38 28.52
08/08/2005 7 2.49 0.01 0.18 2.31 27.60 08/08/2005 7 2.53 0.02 0.17 2.37 28.31
12/08/2005 11 2.45 0.01 0.19 2.26 27.06 12/08/2005 11 2.50 0.00 0.18 2.31 27.67
15/08/2005 14 2.46 0.02 0.10 2.35 28.15 15/08/2005 14 2.31 0.01 0.10 2.22 26.49
18/08/2005 17 2.35 0.01 0.17 2.18 26.06 18/08/2005 17 2.21 0.00 0.15 2.06 24.63
23/08/2005 22 2.43 0.01 0.10 2.34 27.95 23/08/2005 22 2.12 0.01 0.09 2.04 24.34
08/09/2005 37 2.42 0.01 0.10 2.33 27.83 08/09/2005 37 1.98 0.01 0.09 1.89 22.57
09/10/2005 67 2.49 0.01 0.12 2.37 28.38 09/10/2005 67 1.84 0.01 0.23 1.61 19.16
Table 43 Ageing results for 2-ACF at pH 4.6 stored at 0 C for a period of 63 days Table 44 Ageing results for 2-ACF at pH 6.8 stored at 0 C for a period of 63
of analysis days of analysis
128
PH 10.0 PH 4.6
NO MEAN NO MEAN
0 30 0 30
01/08/2005 0 2.40 0.01 0.05 2.35 28.15 01/08/2005 0 2.43 0.02 0.05 2.38 28.42
02/08/2005 1 2.39 0.01 0.11 2.28 27.21 02/08/2005 1 2.55 0.01 0.12 2.43 29.03
03/08/2005 2 2.53 0.01 0.06 2.46 29.48 03/08/2005 2 2.51 0.01 0.08 2.43 29.09
04/08/2005 3 2.55 0.01 0.14 2.41 28.87 04/08/2005 3 2.55 0.03 0.13 2.42 28.96
05/08/2005 4 2.56 0.01 0.15 2.42 28.92 05/08/2005 4 2.55 0.02 0.14 2.41 28.85
06/08/2005 5 2.56 0.02 0.16 2.40 28.66 06/08/2005 5 2.57 0.02 0.15 2.41 28.88
07/08/2005 6 2.59 0.01 0.16 2.42 28.97 07/08/2005 6 2.56 0.00 0.16 2.40 28.70
08/08/2005 7 2.57 0.01 0.17 2.40 28.70 08/08/2005 7 2.53 0.01 0.15 2.38 28.45
12/08/2005 11 2.55 0.02 0.18 2.37 28.37 12/08/2005 11 2.55 0.01 0.16 2.38 28.52
15/08/2005 14 2.46 0.01 0.09 2.37 28.32 15/08/2005 14 2.45 0.01 0.08 2.38 28.42
18/08/2005 17 2.48 0.01 0.14 2.34 27.97 18/08/2005 17 2.45 0.02 0.13 2.32 27.70
23/08/2005 22 2.49 0.01 0.08 2.41 28.78 23/08/2005 22 2.44 0.01 0.07 2.37 28.38
08/09/2005 37 2.42 0.01 0.09 2.34 27.97 08/09/2005 37 2.42 0.01 0.07 2.35 28.05
09/10/2005 67 2.46 0.02 0.16 2.29 27.40 09/10/2005 67 2.48 0.02 0.09 2.39 28.57
Table 45 Ageing results for 2-ACF at pH 10 stored at 0 C for a period of 63 days Table 46 Ageing results for 2-ACF at pH 4.6 stored at 40 C for a period of
of analysis 63 days of analysis
129
PH 6.8 PH 10.0
NO MEAN NO MEAN
0 30 0 30
01/08/2005 0 2.42 0.02 0.05 2.38 28.42 01/08/2005 0 2.40 0.01 0.05 2.35 28.15
02/08/2005 1 2.53 0.02 0.12 2.41 28.79 02/08/2005 1 2.57 0.01 0.11 2.46 29.42
03/08/2005 2 2.50 0.01 0.08 2.42 28.89 03/08/2005 2 2.51 0.01 0.07 2.44 29.25
04/08/2005 3 2.54 0.03 0.13 2.42 28.89 04/08/2005 3 2.55 0.02 0.14 2.41 28.86
05/08/2005 4 2.53 0.01 0.14 2.39 28.64 05/08/2005 4 2.55 0.03 0.15 2.40 28.75
06/08/2005 5 2.56 0.01 0.15 2.41 28.81 06/08/2005 5 2.56 0.01 0.16 2.40 28.72
07/08/2005 6 2.57 0.01 0.16 2.41 28.78 07/08/2005 6 2.55 0.01 0.16 2.39 28.57
08/08/2005 7 2.48 0.13 0.18 2.30 27.51 08/08/2005 7 2.54 0.02 0.17 2.38 28.41
12/08/2005 11 2.53 0.01 0.21 2.32 27.70 12/08/2005 11 2.55 0.03 0.18 2.36 28.28
15/08/2005 14 2.45 0.02 0.14 2.31 27.62 15/08/2005 14 2.43 0.01 0.10 2.33 27.87
18/08/2005 17 2.43 0.02 0.18 2.25 26.92 18/08/2005 17 2.45 0.01 0.15 2.30 27.47
23/08/2005 22 2.42 0.01 0.12 2.30 27.47 23/08/2005 22 2.42 0.01 0.09 2.32 27.79
08/09/2005 37 2.36 0.02 0.15 2.22 26.48 08/09/2005 37 2.40 0.02 0.10 2.30 27.50
09/10/2005 67 2.40 0.02 0.21 2.18 26.08 09/10/2005 67 2.42 0.02 0.14 2.29 27.34
Table 47 Ageing results for 2-ACF at pH 6.8 stored at 40 C for a period of 63 days Table 48 Ageing results for 2-ACF at pH 10 stored at 40 C for a period of 63
130
PH 4.6 PH 6.8
NO MEAN NO MEAN
0 30 0 30
01/08/2005 0 2.43 0.02 0.05 2.38 28.42 01/08/2005 0 2.42 0.02 0.05 2.38 28.42
02/08/2005 1 2.56 0.02 0.12 2.44 29.17 02/08/2005 1 2.54 0.01 0.12 2.42 28.99
03/08/2005 2 2.52 0.02 0.09 2.43 29.09 03/08/2005 2 2.50 0.01 0.08 2.42 28.91
04/08/2005 3 2.60 0.02 0.13 2.47 29.59 04/08/2005 3 2.56 0.01 0.13 2.43 29.06
05/08/2005 4 2.56 0.01 0.14 2.42 28.98 05/08/2005 4 2.53 0.01 0.14 2.39 28.57
06/08/2005 5 2.55 0.02 0.15 2.40 28.69 06/08/2005 5 2.56 0.01 0.15 2.41 28.83
07/08/2005 6 2.54 0.02 0.15 2.38 28.51 07/08/2005 6 2.56 0.02 0.16 2.40 28.69
08/08/2005 7 2.55 0.03 0.15 2.40 28.66 08/08/2005 7 2.54 0.02 0.15 2.39 28.62
12/08/2005 11 2.54 0.02 0.16 2.38 28.50 12/08/2005 11 2.53 0.03 0.16 2.36 28.27
15/08/2005 14 2.44 0.02 0.08 2.36 28.21 15/08/2005 14 2.43 0.02 0.08 2.34 28.03
18/08/2005 17 2.44 0.01 0.14 2.30 27.50 18/08/2005 17 2.43 0.01 0.13 2.30 27.56
23/08/2005 22 2.43 0.02 0.07 2.35 28.16 23/08/2005 22 2.41 0.01 0.07 2.34 27.96
08/09/2005 37 2.39 0.01 0.08 2.30 27.54 08/09/2005 37 2.37 0.01 0.07 2.30 27.46
09/10/2005 67 2.42 0.01 0.16 2.26 27.00 09/10/2005 67 2.39 0.02 0.10 2.29 27.35
Table 49 Ageing results for 2-ACF at pH 4.6 stored at 60 C for a period of 63 days Table 50 Ageing results for 2-ACF at pH 6.8 stored at 60 C for a period of
131
PH 10.0 PH 4.6
NO MEAN NO MEAN
0 30 0 30
01/08/2005 0 2.40 0.01 0.05 2.35 28.15 01/08/2005 0 2.43 0.02 0.05 2.38 28.42
02/08/2005 1 2.54 0.02 0.11 2.43 29.10 02/08/2005 1 2.57 0.01 0.12 2.45 29.27
03/08/2005 2 2.50 0.02 0.05 2.45 29.29 03/08/2005 2 2.51 0.01 0.09 2.43 29.04
04/08/2005 3 2.52 0.02 0.14 2.38 28.52 04/08/2005 3 2.55 0.02 0.14 2.40 28.74
05/08/2005 4 2.50 0.01 0.14 2.35 28.16 05/08/2005 4 2.53 0.02 0.17 2.36 28.24
06/08/2005 5 2.48 0.01 0.16 2.32 27.76 06/08/2005 5 2.54 0.01 0.18 2.36 28.28
07/08/2005 6 2.50 0.02 0.16 2.33 27.89 07/08/2005 6 2.52 0.01 0.20 2.33 27.84
08/08/2005 7 2.50 0.02 0.16 2.34 27.93 08/08/2005 7 2.52 0.02 0.20 2.32 27.71
12/08/2005 11 2.44 0.01 0.17 2.27 27.08 12/08/2005 11 2.52 0.02 0.23 2.29 27.33
15/08/2005 14 2.30 0.01 0.09 2.21 26.45 15/08/2005 14 2.41 0.02 0.17 2.23 26.69
18/08/2005 17 2.26 0.01 0.14 2.12 25.31 18/08/2005 17 2.39 0.01 0.13 2.26 27.02
23/08/2005 22 2.20 0.01 0.08 2.12 25.38 23/08/2005 22 2.37 0.02 0.17 2.20 26.29
08/09/2005 37 2.00 0.01 0.09 1.92 22.86 08/09/2005 37 2.28 0.01 0.15 2.13 25.49
09/10/2005 67 1.76 0.00 0.13 1.63 19.46 09/10/2005 67 1.93 0.03 0.09 1.84 21.99
Table 51 Ageing results for 2-ACF at pH 10 stored at 60 C for a period of 63 days Table 52 Ageing results for 2-ACF at pH 4.6 stored at 80 C for a period of
132
PH 6.8 PH 10.0
NO MEAN NO MEAN
0 30 0 30
01/08/2005 0 2.42 0.02 0.05 2.38 28.42 01/08/2005 0 2.40 0.01 0.05 2.35 28.15
02/08/2005 1 2.55 0.02 0.11 2.44 29.21 02/08/2005 1 2.52 0.01 0.11 2.40 28.75
03/08/2005 2 2.46 0.03 0.08 2.38 28.44 03/08/2005 2 2.41 0.02 0.08 2.34 27.92
04/08/2005 3 2.55 0.02 0.15 2.40 28.69 04/08/2005 3 2.18 0.01 0.14 2.04 24.36
05/08/2005 4 2.50 0.02 0.16 2.34 28.00 05/08/2005 4 2.07 0.01 0.16 1.91 22.84
06/08/2005 5 2.53 0.00 0.17 2.35 28.16 06/08/2005 5 1.98 0.01 0.17 1.81 21.60
07/08/2005 6 2.53 0.01 0.18 2.35 28.11 07/08/2005 6 1.87 0.01 0.18 1.69 20.13
08/08/2005 7 2.49 0.02 0.17 2.32 27.72 08/08/2005 7 1.80 0.02 0.19 1.60 19.10
12/08/2005 11 2.47 0.02 0.18 2.29 27.39 12/08/2005 11 1.51 0.00 0.22 1.29 15.32
15/08/2005 14 2.39 0.01 0.09 2.30 27.52 15/08/2005 14 1.20 0.00 0.17 1.03 12.17
18/08/2005 17 2.35 0.02 0.14 2.21 26.45 18/08/2005 17 0.99 0.00 0.24 0.75 8.77
23/08/2005 22 2.31 0.01 0.09 2.22 26.55 23/08/2005 22 0.87 0.01 0.26 0.61 7.09
08/09/2005 37 2.28 0.02 0.09 2.18 26.08 08/09/2005 37 0.55 0.00 0.07 0.49 5.59
09/10/2005 67 2.21 0.01 0.12 2.09 24.90 09/10/2005 67 0.00 0.00 0.00 0.00 -0.28
Table 53 Ageing results for 2-ACF at pH 6.8 stored at 80 C for a period of 63 days Table 54 Ageing results for 2-ACF at pH 10 stored at 80 C for a period of 63
133
PH 4.6 PH 6.8
NO MEAN NO MEAN
0 30 0 30
01/08/2005 0 2.44 0.01 0.10 2.34 29.64 01/08/2005 0 2.44 0.01 0.15 2.29 28.94
02/08/2005 1 2.40 0.02 0.10 2.30 29.06 02/08/2005 1 2.51 0.01 0.11 2.40 30.37
03/08/2005 2 2.45 0.01 0.11 2.34 29.55 03/08/2005 2 2.52 0.02 0.12 2.40 30.33
04/08/2005 3 2.52 0.02 0.15 2.36 29.87 04/08/2005 3 2.54 0.01 0.14 2.40 30.40
05/08/2005 4 2.44 0.02 0.17 2.28 28.77 05/08/2005 4 2.54 0.02 0.15 2.39 30.27
06/08/2005 5 2.47 0.03 0.17 2.30 29.08 06/08/2005 5 2.55 0.02 0.16 2.39 30.26
07/08/2005 6 2.47 0.02 0.18 2.30 29.03 07/08/2005 6 2.55 0.01 0.17 2.38 30.15
08/08/2005 7 2.49 0.01 0.18 2.31 29.18 08/08/2005 7 2.53 0.02 0.17 2.37 29.93
12/08/2005 11 2.45 0.01 0.19 2.26 28.61 12/08/2005 11 2.50 0.00 0.18 2.31 29.26
15/08/2005 14 2.46 0.02 0.10 2.35 29.76 15/08/2005 14 2.31 0.01 0.10 2.22 28.01
18/08/2005 17 2.35 0.01 0.17 2.18 27.56 18/08/2005 17 2.21 0.00 0.15 2.06 26.06
23/08/2005 22 2.43 0.01 0.10 2.34 29.55 23/08/2005 22 2.12 0.01 0.09 2.04 25.75
08/09/2005 37 2.42 0.01 0.10 2.33 29.42 08/09/2005 37 1.98 0.01 0.09 1.89 23.88
09/10/2005 67 2.49 0.01 0.12 2.37 30.01 09/10/2005 67 1.84 0.01 0.23 1.61 20.29
Table 55 Ageing results for 5-MEF at pH 4.6 stored at 0 C for a period of 63 days Table 56 Ageing results for 5-MEF at pH 6.8 stored at 0 C for a period of 63 of
analysis days of analysis
134
PH 10.0 PH 4.6
NO MEAN NO MEAN
0 30 0 30
01/08/2005 0 2.44 0.01 0.15 2.30 29.05 01/08/2005 0 2.44 0.01 0.10 2.34 29.64
02/08/2005 1 2.52 0.02 0.11 2.41 30.53 02/08/2005 1 2.53 0.01 0.10 2.43 30.75
03/08/2005 2 2.54 0.02 0.12 2.41 30.54 03/08/2005 2 2.53 0.01 0.11 2.42 30.66
04/08/2005 3 2.55 0.02 0.14 2.41 30.52 04/08/2005 3 2.55 0.03 0.13 2.42 30.61
05/08/2005 4 2.56 0.02 0.15 2.42 30.57 05/08/2005 4 2.55 0.02 0.14 2.41 30.50
06/08/2005 5 2.56 0.02 0.16 2.40 30.30 06/08/2005 5 2.57 0.02 0.15 2.41 30.53
07/08/2005 6 2.59 0.03 0.16 2.42 30.63 07/08/2005 6 2.56 0.00 0.16 2.40 30.34
08/08/2005 7 2.57 0.02 0.17 2.40 30.34 08/08/2005 7 2.53 0.01 0.15 2.38 30.08
12/08/2005 11 2.55 0.02 0.18 2.37 30.00 12/08/2005 11 2.55 0.01 0.16 2.38 30.15
15/08/2005 14 2.46 0.01 0.09 2.37 29.94 15/08/2005 14 2.45 0.01 0.08 2.38 30.05
18/08/2005 17 2.48 0.01 0.14 2.34 29.57 18/08/2005 17 2.45 0.02 0.13 2.32 29.29
23/08/2005 22 2.49 0.02 0.08 2.41 30.42 23/08/2005 22 2.44 0.01 0.07 2.37 30.01
08/09/2005 37 2.42 0.02 0.09 2.34 29.58 08/09/2005 37 2.42 0.01 0.07 2.35 29.66
09/10/2005 67 2.46 0.01 0.16 2.29 28.98 09/10/2005 67 2.48 0.02 0.09 2.39 30.21
Table 57 Ageing results for 5-MEF at pH 10 stored at 0 C for a period of 63 days Table 58 Ageing results for 5-MEF at pH 4.6 stored at 40 C for a period of
135
PH 6.8 PH 10.0
NO MEAN NO MEAN
0 30 0 30
01/08/2005 0 2.44 0.01 0.15 2.29 28.94 01/08/2005 0 2.44 0.01 0.15 2.30 29.05
02/08/2005 1 2.52 0.01 0.10 2.41 30.52 02/08/2005 1 2.48 0.01 0.11 2.38 30.03
03/08/2005 2 2.52 0.01 0.11 2.41 30.43 03/08/2005 2 2.52 0.01 0.12 2.39 30.28
04/08/2005 3 2.54 0.03 0.13 2.42 30.54 04/08/2005 3 2.55 0.02 0.14 2.41 30.51
05/08/2005 4 2.53 0.01 0.14 2.39 30.27 05/08/2005 4 2.55 0.03 0.15 2.40 30.39
06/08/2005 5 2.56 0.01 0.15 2.41 30.45 06/08/2005 5 2.56 0.01 0.16 2.40 30.37
07/08/2005 6 2.57 0.01 0.16 2.41 30.43 07/08/2005 6 2.55 0.01 0.16 2.39 30.20
08/08/2005 7 2.48 0.13 0.18 2.30 29.09 08/08/2005 7 2.54 0.02 0.17 2.38 30.04
12/08/2005 11 2.53 0.01 0.21 2.32 29.28 12/08/2005 11 2.55 0.03 0.18 2.36 29.90
15/08/2005 14 2.45 0.02 0.14 2.31 29.21 15/08/2005 14 2.43 0.01 0.10 2.33 29.47
18/08/2005 17 2.43 0.02 0.18 2.25 28.47 18/08/2005 17 2.45 0.01 0.15 2.30 29.05
23/08/2005 22 2.42 0.01 0.12 2.30 29.05 23/08/2005 22 2.42 0.01 0.09 2.32 29.39
08/09/2005 37 2.36 0.02 0.15 2.22 28.00 08/09/2005 37 2.40 0.02 0.10 2.30 29.07
09/10/2005 67 2.40 0.02 0.21 2.18 27.58 09/10/2005 67 2.42 0.02 0.14 2.29 28.91
Table 59 Ageing results for 5-MEF at pH 6.8 stored at 40 C for a period of 63 days Table 60 Ageing results for 5-MEF at pH 10 stored at 40 C for a period of
136
PH 4.6 PH 6.8
NO MEAN NO MEAN
0 30 0 30
01/08/2005 0 2.44 0.01 0.10 2.34 29.64 01/08/2005 0 2.44 0.01 0.15 2.29 28.94
02/08/2005 1 2.52 0.01 0.10 2.42 30.54 02/08/2005 1 2.50 0.02 0.10 2.39 30.25
03/08/2005 2 2.53 0.02 0.11 2.41 30.52 03/08/2005 2 2.53 0.02 0.12 2.42 30.54
04/08/2005 3 2.60 0.02 0.13 2.47 31.28 04/08/2005 3 2.56 0.01 0.13 2.43 30.72
05/08/2005 4 2.56 0.01 0.14 2.42 30.63 05/08/2005 4 2.53 0.01 0.14 2.39 30.20
06/08/2005 5 2.55 0.02 0.15 2.40 30.33 06/08/2005 5 2.56 0.01 0.15 2.41 30.48
07/08/2005 6 2.54 0.02 0.15 2.38 30.14 07/08/2005 6 2.56 0.02 0.16 2.40 30.33
08/08/2005 7 2.55 0.03 0.15 2.40 30.30 08/08/2005 7 2.54 0.02 0.15 2.39 30.26
12/08/2005 11 2.54 0.02 0.16 2.38 30.13 12/08/2005 11 2.53 0.03 0.16 2.36 29.89
15/08/2005 14 2.44 0.02 0.08 2.36 29.82 15/08/2005 14 2.43 0.02 0.08 2.34 29.63
18/08/2005 17 2.44 0.01 0.14 2.30 29.08 18/08/2005 17 2.43 0.01 0.13 2.30 29.14
23/08/2005 22 2.43 0.02 0.07 2.35 29.77 23/08/2005 22 2.41 0.01 0.07 2.34 29.56
08/09/2005 37 2.39 0.01 0.08 2.30 29.12 08/09/2005 37 2.37 0.01 0.07 2.30 29.04
09/10/2005 67 2.42 0.01 0.16 2.26 28.55 09/10/2005 67 2.39 0.02 0.10 2.29 28.92
Table 61 Ageing results for 5-MEF at pH 4.6 stored at 60 C for a period of 63 days Table 62 Ageing results for 5-MEF at pH 6.8 stored at 60 C for period
of analysis of 63 days of analysis
137
PH 10.0 PH 4.6
NO MEAN NO MEAN
0 30 0 30
01/08/2005 0 2.44 0.01 0.15 2.30 29.05 01/08/2005 0 2.44 0.01 0.10 2.34 29.64
02/08/2005 1 2.49 0.01 0.11 2.38 30.06 02/08/2005 1 2.51 0.00 0.12 2.39 30.27
03/08/2005 2 2.51 0.01 0.12 2.38 30.13 03/08/2005 2 2.54 0.01 0.13 2.41 30.47
04/08/2005 3 2.52 0.02 0.14 2.38 30.15 04/08/2005 3 2.55 0.02 0.14 2.40 30.39
05/08/2005 4 2.50 0.01 0.14 2.35 29.77 05/08/2005 4 2.53 0.02 0.17 2.36 29.86
06/08/2005 5 2.48 0.01 0.16 2.32 29.36 06/08/2005 5 2.54 0.01 0.18 2.36 29.90
07/08/2005 6 2.50 0.02 0.16 2.33 29.49 07/08/2005 6 2.52 0.01 0.20 2.33 29.44
08/08/2005 7 2.50 0.02 0.16 2.34 29.53 08/08/2005 7 2.52 0.02 0.20 2.32 29.30
12/08/2005 11 2.44 0.01 0.17 2.27 28.64 12/08/2005 11 2.52 0.02 0.23 2.29 28.90
15/08/2005 14 2.30 0.01 0.09 2.21 27.97 15/08/2005 14 2.41 0.02 0.17 2.23 28.23
18/08/2005 17 2.26 0.01 0.14 2.12 26.77 18/08/2005 17 2.39 0.01 0.13 2.26 28.57
23/08/2005 22 2.20 0.01 0.08 2.12 26.85 23/08/2005 22 2.37 0.02 0.17 2.20 27.81
08/09/2005 37 2.00 0.01 0.09 1.92 24.19 08/09/2005 37 2.28 0.01 0.15 2.13 26.96
09/10/2005 67 1.76 0.00 0.13 1.63 20.61 09/10/2005 67 1.93 0.03 0.09 1.84 23.28
Table 63 Ageing results for 5-MEF at pH 10 stored at 60 C for a period of 63 days Table 64 Ageing results for 5-MEF at pH 4.6 stored at 80 C for a period of
138
PH 6.8 PH 10.0
NO MEAN NO MEAN
0 30 0 30
01/08/2005 0 2.44 0.01 0.15 2.29 28.94 01/08/2005 0 2.44 0.01 0.15 2.30 29.05
02/08/2005 1 2.48 0.01 0.13 2.35 29.72 02/08/2005 1 2.37 0.01 0.11 2.26 28.56
03/08/2005 2 2.52 0.01 0.13 2.39 30.22 03/08/2005 2 2.28 0.01 0.13 2.16 27.25
04/08/2005 3 2.55 0.02 0.15 2.40 30.33 04/08/2005 3 2.18 0.01 0.14 2.04 25.77
05/08/2005 4 2.50 0.02 0.16 2.34 29.61 05/08/2005 4 2.07 0.01 0.16 1.91 24.17
06/08/2005 5 2.53 0.00 0.17 2.35 29.77 06/08/2005 5 1.98 0.01 0.17 1.81 22.86
07/08/2005 6 2.53 0.01 0.18 2.35 29.72 07/08/2005 6 1.87 0.01 0.18 1.69 21.32
08/08/2005 7 2.49 0.02 0.17 2.32 29.31 08/08/2005 7 1.80 0.02 0.19 1.60 20.22
12/08/2005 11 2.47 0.02 0.18 2.29 28.96 12/08/2005 11 1.51 0.00 0.22 1.29 16.25
15/08/2005 14 2.39 0.01 0.09 2.30 29.10 15/08/2005 14 1.20 0.00 0.17 1.03 12.93
18/08/2005 17 2.35 0.02 0.14 2.21 27.97 18/08/2005 17 0.99 0.00 0.24 0.75 9.34
23/08/2005 22 2.31 0.01 0.09 2.22 28.08 23/08/2005 22 0.87 0.01 0.26 0.61 7.57
08/09/2005 37 2.28 0.02 0.09 2.18 27.59 08/09/2005 37 0.55 0.00 0.07 0.49 6.00
09/10/2005 67 2.21 0.01 0.12 2.09 26.34 09/10/2005 67 0.00 0.00 0.00 0.00 -0.19
Table 65 Ageing results for 5-MEF at pH 6.8 stored at 80 C for a period of 63 days Table 66 Ageing results for 5-MEF at pH 10 stored at 80 C for a period of
139
PH 4.6 PH 6.8
NO MEAN NO MEAN
0 30 0 30
31/07/2005 0 2.48862 0.014 1.8409 0.64772 9.9965385 31/07/2005 0 1.80052 0.015 0.069 1.73152 30.838846
01/08/2005 1 2.4694 0.013 1.8747 0.5947 8.9769231 01/08/2005 1 1.97308 0.014 0.2143 1.75878 31.363077
02/08/2005 2 2.4806 0.017 1.8957 0.5849 8.7884615 02/08/2005 2 2.01756 0.017 0.2272 1.79036 31.970385
03/08/2005 3 2.55792 0.009 1.9026 0.65532 10.142692 03/08/2005 3 2.0966 0.015 0.3171 1.7795 31.761538
04/08/2005 4 2.48616 0.014 1.8333 0.65286 10.095385 04/08/2005 4 2.07552 0.013 0.3959 1.67962 29.840769
05/08/2005 5 2.5014 0.008 1.799 0.7024 11.048077 05/08/2005 5 2.03994 0.004 0.4063 1.63364 28.956538
06/08/2005 6 2.5166 0.014 1.804 0.7126 11.244231 06/08/2005 6 2.04824 0.008 0.5318 1.51644 26.702692
07/08/2005 7 2.54786 0.024 1.8074 0.74046 11.78 07/08/2005 7 2.04734 0.014 0.6179 1.42944 25.029615
10/08/2005 10 2.53974 0.020 1.7204 0.81934 13.296923 10/08/2005 10 2.08842 0.010 0.7405 1.34792 23.461923
13/08/2005 13 2.43758 0.012 1.7083 0.72928 11.565 13/08/2005 13 1.99668 0.023 0.9039 1.09278 18.555385
16/08/2005 16 2.44942 0.018 1.5284 0.92102 15.252308 16/08/2005 16 2.01286 0.010 0.8353 1.17756 20.185769
19/08/2005 19 2.32178 0.029 1.4707 0.85108 13.907308 19/08/2005 19 1.8242 0.014 0.8761 0.9481 15.773077
22/08/2005 21 2.41804 0.013 1.4561 0.96194 16.039231 22/08/2005 21 1.92942 0.009 0.9474 0.98202 16.425385
30/08/2005 25 2.42456 0.030 1.3724 1.05216 17.774231 30/08/2005 25 1.9854 0.007 0.9282 1.0572 17.871154
06/09/2005 31 2.44452 0.015 1.4662 0.97832 16.354231 06/09/2005 31 1.99878 0.007 1.0266 0.97218 16.236154
09/10/2005 63 2.45 0.020 1.4294 1.0206 17.167308 09/10/2005 63 2.01418 0.014 1.1182 0.89598 14.770769
Table 67 Ageing results for FOL at pH 4.6 stored at 0 C for a period of 63 days Table 68 Ageing results for FOL at pH 6.8 stored at 0 C for a period 63
140
PH 10.0 PH 4.6
NO MEAN NO MEAN
0 30 0 30
31/07/2005 0 2.3119 0.024 1.0981 1.2138 20.882692 01/08/2005 0 2.48862 0.014 1.8409 0.64772 9.9965385
01/08/2005 1 2.33102 0.012 0.9223 1.40872 24.631154 02/08/2005 1 2.39616 0.023 1.8689 0.52726 7.68
02/08/2005 2 2.33766 0.015 0.965 1.37266 23.937692 03/08/2005 2 2.50348 0.027 1.8994 0.60408 9.1573077
03/08/2005 3 2.37826 0.014 0.87798 1.50028 26.391923 04/08/2005 3 2.52472 0.019 1.9463 0.57842 8.6638462
04/08/2005 4 2.32758 0.010 0.7942 1.53338 27.028462 05/08/2005 4 2.49676 0.008 1.922 0.57476 8.5934615
05/08/2005 5 2.33726 0.009 0.7995 1.53776 27.112692 06/08/2005 5 2.52124 0.003 1.9085 0.61274 9.3238462
06/08/2005 6 2.3399 0.016 0.7215 1.6184 28.663462 07/08/2005 6 2.54578 0.030 1.9358 0.60998 9.2707692
07/08/2005 7 2.35756 0.022 0.7406 1.61696 28.635769 10/08/2005 9 2.52704 0.021 1.9626 0.56444 8.395
10/08/2005 10 2.35236 0.018 0.6619 1.69046 30.049231 13/08/2005 10 2.56706 0.022 1.9312 0.63586 9.7684615
13/08/2005 13 2.27722 0.023 0.6196 1.65762 29.417692 16/08/2005 15 2.4911 0.025 1.9885 0.5026 7.2057692
16/08/2005 16 2.29408 0.007 0.4525 1.84158 32.955385 19/08/2005 18 2.47894 0.015 1.831 0.64794 10.000769
19/08/2005 19 2.1265 0.010 0.4131 1.7134 30.490385 22/08/2005 21 2.33652 0.024 1.8128 0.52372 7.6119231
22/08/2005 21 2.24818 0.006 0.3578 1.89038 33.893846 30/08/2005 28 2.43722 0.022 1.7861 0.65112 10.061923
30/08/2005 25 2.25766 0.015 0.3565 1.90116 34.101154 06/09/2005 31 2.45264 0.036 1.7966 0.65604 10.156538
06/09/2005 31 2.27986 0.008 0.3435 1.93636 34.778077 09/10/2005 63 2.45302 0.023 1.8132 0.63982 9.8446154
09/10/2005 63 2.31926 0.013 0.3496 1.96966 35.418462
Table 69 Ageing results for FOL at pH 10 stored at 0 C for a period of 63 days Table 70 Ageing results for FOL at pH 4.6 stored at 40 C for a period of 63
141
PH 6.8 PH 10.0
NO MEAN NO MEAN
0 30 0 30
01/08/2005 0 1.80052 0.015 0.069 1.73152 30.838846 01/08/2005 0 2.3119 0.024 1.0981 1.2138 20.882692
02/08/2005 1 2.00702 0.011 0.1755 1.83152 32.761923 02/08/2005 1 2.31026 0.015 0.9223 1.38796 24.231923
03/08/2005 2 2.04046 0.004 0.2246 1.81586 32.460769 03/08/2005 2 2.35634 0.008 0.8897 1.46664 25.745
04/08/2005 3 2.07448 0.009 0.2117 1.86278 33.363077 04/08/2005 3 2.3502 0.024 0.9314 1.4188 24.825
05/08/2005 4 2.06124 0.004 0.2304 1.83084 32.748846 05/08/2005 4 2.3359 0.014 0.9147 1.4212 24.871154
06/08/2005 5 2.0364 0.003 0.2458 1.7906 31.975 06/08/2005 5 2.35366 0.009 0.9309 1.42276 24.901154
07/08/2005 6 2.04828 0.010 0.2832 1.76508 31.484231 07/08/2005 6 2.34626 0.009 0.9301 1.41616 24.774231
10/08/2005 9 2.05172 0.012 0.3469 1.70482 30.325385 10/08/2005 9 2.36026 0.010 0.9551 1.40516 24.562692
13/08/2005 10 2.06056 0.013 0.3819 1.67866 29.822308 13/08/2005 10 2.38094 0.011 0.9698 1.41114 24.677692
16/08/2005 15 2.00346 0.007 0.4635 1.53996 27.155 16/08/2005 15 2.29032 0.015 0.9588 1.33152 23.146538
19/08/2005 18 1.98524 0.012 0.3618 1.62344 28.760385 19/08/2005 18 2.30116 0.017 0.8327 1.46846 25.78
22/08/2005 21 1.8196 0.010 0.3871 1.4325 25.088462 22/08/2005 21 2.11402 0.005 0.8008 1.31322 22.794615
30/08/2005 25 1.93192 0.005 0.4408 1.49112 26.215769 30/08/2005 25 2.25958 0.021 0.7752 1.48438 26.086154
06/09/2005 31 1.95228 0.011 0.3744 1.57788 27.884231 06/09/2005 31 2.28052 0.010 0.7717 1.50882 26.556154
09/10/2005 63 1.95 0.011 0.4523 1.4977 26.34 09/10/2005 63 2.2574 0.021 0.8229 1.4345 25.126923
Table 71 Ageing results for FOL at pH 6.8 stored at 40 C for a period of 63 days Table 72 Ageing results for FOL at pH 10 stored at 40 C for a period of 63
142
PH 4.6 PH 6.8
NO MEAN NO MEAN
0 30 0 30
01/08/2005 0 2.48862 0.014 1.8409 0.64772 9.9965385 01/08/2005 0 1.80052 0.015 0.069 1.73152 30.838846
02/08/2005 1 2.41058 0.016 1.904 0.50658 7.2823077 02/08/2005 1 1.97578 0.010 0.1495 1.82628 32.661154
03/08/2005 2 2.51262 0.013 1.9725 0.54012 7.9273077 03/08/2005 2 2.02646 0.015 0.1825 1.84396 33.001154
04/08/2005 3 2.54842 0.013 1.9601 0.58832 8.8542308 04/08/2005 3 2.06574 0.011 0.1974 1.86834 33.47
05/08/2005 4 2.51518 0.032 1.9738 0.54138 7.9515385 05/08/2005 4 2.0633 0.012 0.2063 1.857 33.251923
06/08/2005 5 2.52848 0.009 1.965 0.56348 8.3765385 06/08/2005 5 2.0294 0.002 0.2302 1.7992 32.140385
07/08/2005 6 2.5489 0.013 1.9944 0.5545 8.2038462 07/08/2005 6 2.03488 0.008 0.2489 1.78598 31.886154
10/08/2005 9 2.56202 0.018 2.0646 0.49742 7.1061538 10/08/2005 9 2.05742 0.013 0.3074 1.75002 31.194615
13/08/2005 10 2.56614 0.024 2.0623 0.50384 7.2296154 13/08/2005 10 2.04866 0.004 0.282 1.76666 31.514615
16/08/2005 15 2.4799 0.020 2.1035 0.3764 4.7788462 16/08/2005 15 1.96766 0.012 0.31 1.65766 29.418462
19/08/2005 18 2.49778 0.016 2.0125 0.48528 6.8726923 19/08/2005 18 1.977 0.008 0.1785 1.7985 32.126923
22/08/2005 21 2.35924 0.018 2.0173 0.34194 4.1161538 22/08/2005 21 1.8073 0.007 0.1801 1.6272 28.832692
30/08/2005 28 2.46872 0.016 2.0415 0.42722 5.7561538 30/08/2005 25 1.92836 0.005 0.1568 1.77156 31.608846
06/09/2005 31 2.48522 0.022 2.2069 0.27832 2.8926923 06/09/2005 31 1.93058 0.012 0.1609 1.76968 31.572692
09/10/2005 63 2.49522 0.024 2.2742 0.22102 1.7907692 09/10/2005 63 1.93108 0.009 0.1872 1.74388 31.076538
Table 73 Ageing results for FOL at pH 4.6 stored at 60 C for a period of 63 days Table 74 Ageing results for FOL at pH 6.8 stored at 60 C for a period of 63
143
PH 10.0 PH 4.6
NO MEAN NO MEAN
0 30 0 30
01/08/2005 0 2.3119 0.024 1.0981 1.2138 20.882692 01/08/2005 0 2.48862 0.014 1.8409 0.64772 9.9965385
02/08/2005 1 2.31008 0.003 0.9223 1.38778 24.228462 02/08/2005 1 2.42418 0.014 1.8577 0.56648 8.4342308
03/08/2005 2 2.34186 0.019 0.9545 1.38736 24.220385 03/08/2005 2 2.53476 0.022 1.9827 0.55206 8.1569231
04/08/2005 3 2.3407 0.020 0.9602 1.3805 24.088462 04/08/2005 3 2.55482 0.020 2.0684 0.48642 6.8946154
05/08/2005 4 2.34302 0.006 0.9888 1.35422 23.583077 05/08/2005 4 2.56966 0.025 2.0904 0.47926 6.7569231
06/08/2005 5 2.34918 0.007 0.9715 1.37768 24.034231 06/08/2005 5 2.57518 0.010 2.0985 0.47668 6.7073077
07/08/2005 6 2.36166 0.015 0.9919 1.36976 23.881923 07/08/2005 6 2.60736 0.025 2.2222 0.38516 4.9473077
10/08/2005 9 2.35676 0.015 1.0118 1.34496 23.405 10/08/2005 9 2.61906 0.031 2.2806 0.33846 4.0492308
13/08/2005 10 2.3917 0.007 1.0613 1.3304 23.125 13/08/2005 10 2.64646 0.021 2.4921 0.15436 0.5088462
16/08/2005 15 2.29816 0.008 1.0517 1.24646 21.510769 16/08/2005 15 2.59904 0.030 2.5919 0.00714 -2.3223077
19/08/2005 18 2.28784 0.019 0.9429 1.34494 23.404615 19/08/2005 18 2.60384 0.015 2.5177 0.08614 -0.8030769
22/08/2005 21 2.13628 0.011 0.9293 1.20698 20.751538 22/08/2005 21 2.45194 0.031 2.33889 0.11305 -0.2855769
30/08/2005 25 2.2568 0.017 0.8956 1.3612 23.717308 30/08/2005 28 2.57132 0.016 2.5868 -0.01548 -2.7573077
06/09/2005 31 2.28542 0.012 0.9468 1.33862 23.283077 06/09/2005 31 2.65134 0.025 2.6807 -0.02936 -3.0242308
09/10/2005 63 2.2675 0.025 0.9028 1.3647 23.784615 09/10/2005 63 2.62634 0.018 2.6505 -0.02416 -2.9242308
Table 75 Ageing results for FOL at pH 10 stored at 60 C for a period of 63 days Table 76 Ageing results for FOL at pH 4.6 stored at 80 C for a period of
144
PH 6.8 PH 10.0
NO MEAN NO MEAN
0 30 0 30
01/08/2005 0 1.80052 0.015 0.069 1.73152 30.838846 01/08/2005 0 2.3119 0.024 1.0981 1.2138 20.882692
02/08/2005 1 1.96916 0.006 0.1682 1.80096 32.174231 02/08/2005 1 2.37694 0.015 0.9223 1.45464 25.514231
03/08/2005 2 2.03392 0.012 0.1875 1.84642 33.048462 03/08/2005 2 2.34028 0.016 0.9941 1.34618 23.428462
04/08/2005 3 2.07342 0.011 0.1969 1.87652 33.627308 04/08/2005 3 2.3425 0.022 1.0111 1.3314 23.144231
05/08/2005 4 2.05588 0.011 0.2169 1.83898 32.905385 05/08/2005 4 2.34154 0.019 1.0229 1.31864 22.898846
06/08/2005 5 2.03486 0.008 0.2412 1.79366 32.033846 06/08/2005 5 2.34594 0.007 1.0361 1.30984 22.729615
07/08/2005 6 2.03442 0.006 0.2622 1.77222 31.621538 07/08/2005 6 2.36812 0.003 1.086 1.28212 22.196538
10/08/2005 9 2.05696 0.018 0.3203 1.73666 30.937692 10/08/2005 9 2.35394 0.021 1.1061 1.24784 21.537308
13/08/2005 10 2.05016 0.007 0.2989 1.75126 31.218462 13/08/2005 10 2.39286 0.032 1.4171 0.97576 16.305
16/08/2005 15 1.9935 0.015 0.3199 1.6736 29.725 16/08/2005 15 2.31422 0.020 1.5972 0.71702 11.329231
19/08/2005 18 2.01042 0.017 0.1775 1.83292 32.788846 19/08/2005 18 2.32952 0.020 1.7296 0.59992 9.0773077
22/08/2005 21 1.87114 0.006 0.1818 1.68934 30.027692 22/08/2005 21 2.20646 0.016 2.0194 0.18706 1.1376923
30/08/2005 25 1.97938 0.014 0.1561 1.82328 32.603462 30/08/2005 25 2.32484 0.022 2.509 -0.18416 -6.0011538
06/09/2005 31 2.0491 0.014 0.1654 1.8837 33.765385 06/09/2005 31 2.49928 0.030 2.6999 -0.20062 -6.3176923
09/10/2005 63 2.00466 0.006 0.2011 1.80356 32.224231 09/10/2005 63 2.37316 0.013 2.2159 0.15726 0.5646154
Table 77 Ageing results for FOL at pH 6.8 stored at 80 C for a period of 63 days Table 78 Ageing results for FOL at pH 10 stored at 80 C for a period of
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Teza Furan Christofidis-2007

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Cranfield University

Academic Year 2004/2006

Analytical Methods For Assessing Paper Degradation In Transformers

Power transformers are essential equipments for distributing electricity.

Generally, the operation theory of a transformer is based upon three principles:

A voltage is delivered to the primary winding via a conductor, which

This secondary winding current is used as an output of the electrical

There are many different types of transformers including: Generator transformers;

When it comes to the production of a transformer the designer and the

The insulating material of a transformer mainly consists of cellulosic paper

1.2 Insulating oil

Solid insulation of a transformer is commonly provided by cellulosic paper

Insulating paper consists of 76-86% w/w cellulose, 10-15% w/w hemi

Before the paper is introduced to the transformer, there is in a high necessity to

International Material Standards also exist to establish the requirements for

Insulation paper is a key material to the operational life-time of a transformer.

1.4 Degradation of Insulating paper

1.4.1 The Paper Degradation Process

As mentioned above, degradation of paper is a result of the reduction of the

Figure 1 Cellulose; Two units of D-anhydroglucopyranose joined together by β-1,4-glycosidic

In general the process of cellulosic degradation involves a chain scission or

1.4.1.1 Effect of Temperature

Cellulose, under higher temperature (to a maximum of 200˚C) tends to be

Figure 2 Thermal degradation of insulating paper

1.4.1.2 Effect of Oxygen

Figure 3 Oxidation of Cellulose

1.4.1.3. Effect of Moisture

Figure 4 Hydrolytic degradation of cellulose

1.5 Furanic compounds

Furan is the parent compound of these five membered ring structures

Furan 5-hydroxymethyl-2-furfuraldehyde 2-furfuraldehyde

COCH3 H3C CHO CH2OH

2-acetyl furan 5-methyl-2-furfuraldehyde furfuryl alcohol

Figure 5 furan and derivatives

Figure 9 Production of furan from pentose (adapted from R.O.C Norman).[23]

It is known that degradation of cellulosic insulating paper by the factors and

(Chendong) DP= (1.51-Log102-FAL)/0.0035 (1)

DPmin=800/ (0.186*2-Fal) +1 [27]

Assuming a variation of ±50% from the average, the range of degradation of

Another relationship which has been established is between the gases

Although there is significant evidence regarding how furans are produced

It is essential that such research be conducted due to a number of problems

However, before the investigation how these compounds can be detected it is

To define a set of standard parameters under which furanic samples

To investigate the five furan derivatives in respect to key physical

To examine the furan degradation process and the production of other

To investigate the recovery and distribution of the furanic compounds

IDENTIFICATION OF FURANIC COMPOUNDS

The aim of this chapter is to conduct an initial examination, in order to gain

The different analytical techniques that can be used for the

Which technique is most suited to proceed with the later experiments.

Calibration information for each furan derivative, by means of

3.2.0 Materials and Methods

3.2.1 General Materials

Furfuryl alcohol 99%, Content: 50 g, Lot No: 09675-036, Cat. No:

2-Acetyl Furfural 99%, Content: 25 g, Lot No: 12865-076, Cat No:

5-Hydroxymethyl Furfural, Content: 5 g, Lot No: 11499-066, Cat No:

2-Furaldehyde 99%, Content: 25g, Lot No: 60712-018, Cat No:

Tetrachloroethylene 99%, Content: 2.5L, Lot No: 0273725, Cat No:

3.2.2 Method for the Maximum Absorbance

3.2.3 Calibration and Analysis Using HPLC, Infrared and

Once the maximum wavelength of absorbance was determined, a series of